Transparent plastic material, optical article based on the material, and production method thereof

ABSTRACT

A transparent plastic material and an optical article formed of the material which have no variation in color, no generation of precipitation, properties to selectively absorb only light of a specific wavelength, selectively block or reduce light of a wavelength which is dazzling to human eyes, and block harmful ultraviolet light. A transparent plastic material includes a polymer obtained by polymerizing one or more polymerizable monomersin the presence of a polymerization initiator or polymerization catalyst, wherein the polymer contains a complex compound of Formula (I): 
     
         A.sub.2 M(OH)(H.sub.2 O)                                   (I) 
    
     wherein M denotes Sc, Y, La, Pt, Nd, Pm, Sm, Gd, Dy, Ho, Er, Tm, or Lu; A is a ligand for forming a chelate complex having a structure shown below ##STR1## and containing at least one of an aryl group and a heterocyclic group.

FIELD OF THE INVENTION

This invention relates to a transparent plastic material whichselectively blocks only light of a specific wavelength and having thefunction to blocking ultraviolet which does harm to human eyes andselectively blocking or reducing light of a specific wavelength which isdazzling to the human eye, easier to be manufactured and lighter thanconventional materials and stable over time, and an optical articlecomprising the material.

BACKGROUND OF THE INVENTION

When adapted to light, the human eye perceives light in the vicinity of555 nm (520 to 590 nm) in wavelength to be the brightest, and whenadapted to the dark, the human eye perceives light in the vicinity of507 nm (472 to 542 nm) in wavelength to be the brightest. This is thereason why a person feels dazzled when he rapidly enters a dark placefrom a dark place or, to the contrary, nothing is visible for a timewhen he enters a light place from a dark place. Further, the abovephenomenon is also the reason why he feels very dazzled under strongsunlight such as outdoors in the daytime during fine weather, at theseashore or mountains in summer. As a result, to prevent such glare,sunglasses are generally used. However, since sunglasses use onlycolored lenses, the sight becomes dark. Further, those lenses which donot appropriately absorb ultraviolet light (do not block ultravioletlight) expand the pupil due to the darkness of the sight allowing theamount of ultraviolet light entering the eye to increase. Thisultraviolet light is harmful to the human eye, and light of 280 to 315nm in wavelength (UV-B) is said to be absorbed by the cornea to causedifficulties for the cornea such as inflammation of the cornea. Further,ultraviolet light of 300 to 400 nm in wavelength (UV-A) is said to reachthe lens of the eye and is absorbed, and extended exposure toultraviolet light is considered to be a cause of senile cataract.Therefore, sunglasses which do not cut ultraviolet light cause heavyphysiological burden to the eyes. Further, to prevent the occurrence ofcataract, it is necessary to cut ultraviolet light which is harmful tothe lens of the eye.

Neodymium compounds, which are rare earth compounds, have a sharpabsorption in the vicinity of 570 to 590 nm and can selectively absorbonly light of wavelengths which are dazzling to human eyes. Therefore,utilizing these properties, neodymium compounds are incorporated intoglass to endow eyeglass lenses and automobile mirrors with glare-proofproperties. At the same time, introduction of neodymium compounds intotransparent plastics to obtain highly transparent optical plastics withglare-proof properties has been investigated. Some examples are givenbelow:

(1) Japanese Patent Publication 42-3949/1967

This patent discloses a method for producing a light blocker in which anorganic thin film from a water-soluble polyether containing awater-soluble rare earth metal salt such as neodymium or cerium isattached to the inner surface of a mold comprising glass or a metal, anda inethacrylic ester or an acrylic ester and a prepolymer of ana,b-unsaturated carboxylic acid are injected into a mold, followed byheat polymerization.

(2) Japanese Patent Laid-open Publication (OPI)51-56851/1976

This patent discloses a resin composition comprising an inorganicneodymium compound such as neodymium phosphate, neodymium carbonate,neodymium sulfate, neodymium oxide, or neodymium nitrate mixed with asynthetic resin.

(3) Japanese OPI 51-58444/1976

This patent discloses a resin composition comprising an organicneodymium compound such as neodymium ethylenediamine-tetraacetate,neodymium acetate, or neodymium stearate mixed into a synthetic resinsuch as methylmethacrylate resin or styrene resin.

(4) Japanese OPI 58-225148/1983

This patent proposes a selective light absorbing resin composition forthe visible light region comprising particles of a neodymium compoundsuch as neodymium oxide, neodymium hydroxide, neodymium carbonate,neodymium phosphate, neodymium sulfate, neodymium chloride, or neodymiumacetate having an average particle diameter of 0.2 to 20 μm dispersed ina transparent plastic base material.

However, conventional neodymium compounds such as neodymium oxide,neodymium carbonate, neodymium chloride, neodymium nitrate, neodymiumsulfate, neodymium sulfide, neodymium oxalate, and neodymium acetate areless compatible with and sparingly soluble in typical polymerizablemonomers such as diethyleneglycolbisallylcarbonate, methylmethacrylate,and styrene which form transparent plastics.

Therefore, when the inorganic neodymium compound of (2) is kneaded withan organic synthetic resin such as a methylmethacrylate resin or astyrene resin, uniform mixing is difficult because of insufficientcompatibility of the materials.

With the organic neodymium compound of (3), when it is heated andkneaded with methylmethacrylate resin, uniform dispersion is difficultand a transparent resin material is not obtained.

With (4), since the total light transmissivity is low too, a highlytransparent resin is not obtained.

(5) Japanese Patent Publication 44-5091/1969

This patent proposes that, since neodymium acetate is less compatiblewith methylmethacrylate resin, a method in which the neodymium salt ismade compatible with methylmethacrylate using anhydrous stannic chlorideas a solvent, which is cast by heat polymerization.

However, this method is not only high in cost since casting is madeusing stannic chloride as a solvent, but also the resulting resin is notcompletely transparent because of a turbidity due to the dispersed fineparticles, and has problems of low weather resistance and tendency todevitrification.

The other way obtaining optical elements is also proposed here,in whichwater soluble metallic salt such as neodymium acetate, neodymiumchloride,neodymium nitrate,neodymium sulfate,or stealilic neodymium isdissolved in hydrophilic monomers such as2-hydroxyethylmethacrylate,methacrylic acid, or acrylic acid,and is usedtogether with the other hydrophobic monomers.

(6) Japanese OPI 01-161024/1989

This patent discloses a method in which, making use of the fact thatneodymium nitrate, which is considered to be less compatible withpolymerizable monomers, is soluble in 2-hydroxyethylmethacrylate, thesolution is mixed with methylmethacrylate or acryl-diglycolcarbonate asa monomer, or mixed with polyvinylalcohol as a polymer, and heatpolymerized to form a glare-proof plate or film. Furthermore,2-hydroxyethylmethacrylate must always be present, which tends toadversely effect the properties of the resulting polymer. Specifically,since a polymer containing 2-hydroxyethylmethacrylate has thedisadvantages of high water absorption and poor thermal characteristics,the polymer tends to deform due to water absorption or on heating.Especially for optical elements, since deformation directly affects theoptical characteristics, deformation should be as small as possible.Moreover, in many cases, optical elements are renderd anti-reflectiveeffect by forming an inorganic deposited film on the surface of thetransparent plastic material. However, when deformation occurs in thesubstrate, the stress produces cracks in the deposited film, which leadsto a degradation in optical performance.

(7) Japanese OPI 02-153301

This patent discloses a plastic-based optical element comprising apolymer obtained by polymerizing a monomer mixture containing at leastone neodymium compound selected from the group consisting of neodymiumacrylate and neodymium methacrylate, at least one unsaturated carboxylicacid selected from the group consisting of acrylic acid and methacrylicacid, and styrene or a styrene derivative.

In this method, since acrylic acid or methacrylic acid are copresent,the polymer has high water absorptivity and has similar problems as themethod (6).

(8) Japanese Patent Publication 05-64179/1993

This patent proposes a production method for a rare earth elementcontaining resin composition which has superior selective absorption ofradiation and electromagnetic waves, characterized in that a mixture ofa resin mainly comprising methacrylic acid ester, at least one rareearth element compound selected from the group consisting of the oxide,hydroxide, complex, or salt of inorganic acid of lanthanum, cerium,praseodymium, dysprosium, thulium, ytterbium, and lutetium, at least onesolvent selected from the group consisting of compounds of the formulaR₁ --COOH solubilie in the above two components (wherein R₁ is asaturated or unsaturated hydrocarbon residue of 1 to 20 carbon atoms);R₂ --OCO--R₃ --COOH (wherein R₂ is a hydrogen atom or a hydrocarbonresidue of 1 to 9 carbon atoms, R₃ is a saturated or unsaturatedhydrocarbon residue of 1 to 4 carbon atoms); CH₂ ═(R₄)--COO--(--A₁--O--)nH (wherein R₄ is a hydrogen atom or a methyl group, A₁ is analkylene group of 2 to 6 carbon atoms, and n is 0 or an integer from 1to 10); CH₂ ═C(R₅)--COO--R₆ --OH (wherein R₅ is a hydrogen atom or amethyl group, R₆ an alkylene group of 2 to 6 carbon atoms); R₇ --OH(wherein R₇ is a saturated or unsaturated hydrocarbon residue of 3 to 10carbon atoms); and R₈ --(--A₂ --O--)nH (wherein R₈ is a hydroxy group ora saturated or unsaturated hydrocarbon residue of 1 to 10 carbon atoms,A₂ is an alkylene group of 2 to 4 carbon atoms, and m is an integer from1 to 10), and a polymerization initiator is polymerized in a mold.

However, since this method uses an unsaturated carboxylic acid such asmethacrylic acid or acrylic acid, a saturated or unsaturated fatty acidsuch as propionic acid, isobutyric acid, n-butyric acid, caproic acid,caprylic acid, capric acid, 2-ethylhexanoic acid, stearic acid, ornaphthenic acid, an unsaturated alcohol such as α-hydroxyethylacrylateor α-hydroxyethylmethacrylate; a saturated aliphatic alcohol such aspropylenealcohol or cyclohexylalcohol, or a polyhydric alcohol such asethyleneglycol, diethyleneglycol, or propyleneglycol, is used as aco-solvent to uniformly dissolve the rare earth element compound in theresin material, therefore the resin has an increased water absorptivityand tends to have problems similar to those shown in the method (6).

(9) Japanese Patent Publication 05-52325/1993

This patent discloses a production method of a neodymium containingtransparent resin in which in a mixture of one monomer selected from thegroup consisting of alkylmethacrylate, the alkyl group having 1 to 4carbon atoms, and styrene, at least one compound selected from the groupconsisting of acrylic acid and/or methacrylic acid, and a saturated orunsaturated organic carboxylic acid of 6 to 20 carbon atoms which may besubstituted with a hydroxyl group or an alkoxycarbonyl group, and water,a water-soluble inorganic strong acid salt of neodymium and awater-soluble inorganic acid are reacted in a ratio satisfying aspecified range to obtain a monomer composition, and the monomercomposition, as is, is polymerized.

However, since this method also uses acrylic acid and/or methacrylicacid as in method (7), and further at least one compound selected fromthe group consisting of saturated or unsaturated organic carboxylicacids of 6 to 20 total carbon atoms which may be substituted with ahydroxy group or an alkoxycarbonyl group and a water-soluble inorganicacid salt of neodymium, the resin has a high water absorptivity and thushas problems similar to those of method (6).

(10) Japanese Patent Publication 05-79684/1993

This patent discloses a neodymium containing transparent resin which isa reaction product comprising at least one compound selected from thegroup consisting of a copolymer comprising a monomer comprising styrenealone or an alkylmethacrylate of 1 to 4 carbon atoms mainly comprisingstyrene and at least one compound selected from the group consisting ofacrylic acid, methacrylic acid, neodymium acrylate and neodymiummethacrylate, and neodymium salt thereof, wherein the number of carboxylgroups of the organic carboxylic acid and salt thereof to the totalnumber of carboxyl group of the acrylic acid, methacrylic acid, and saltthereof is x, and the ratio of carboxyl groups forming a saltneutralizing neodymium of all of the carboxyl groups is y, and x and ysatisfy one of the following formulas I, II, and III.

Formula 1!

    0.05≦y≦(5/2)x+0.2, 0≦x≦0.3     (Formula I)

    0.05≦y≦-(5/2)(x-0.3)+0.95, 0.3≦x≦0.05(Formula II)

    0.05≦y≦-(8/3)(x-0.55)+0.85 0.55≦x≦0.85(Formula III)

However, in this method, since methacrylic acid, acrylic acid, or asaturated or unsaturated organic carboxylic acid of 6 to 21 carbon atomsunsubstituted or substituted with a hydroxy group is present, the resinalso has problems similar to those of method (6).

As described above, rare earth compounds such as conventional neodymiumcompounds have problems of poor compatibility with hydrophobicpolymerizable monomers. The various methods set forth above have beenused to eliminate such problems, but these methods have problems ofwater absorption by the resins, and are thus defective in dimensionalstability when used as optical elements. On the other hand, transparentmaterials such as eyeglass lenses and contact lenses contain ultravioletabsorbers to block ultraviolet light. However, ultraviolet absorberstend to have problems in terms of compatibility with polymerizablemonomers, but use of several types of additives or large amounts ofultraviolet absorbers deteriorates the mechanical characteristics of thepolymers. Also when transparent plastic materials having a glare-prooffunction are used in eyeglass lenses or contact lenses, compounds havinga glare-proof function and ultraviolet absorbers must generally be addedto the polymerizable monomers for the above purpose, which may haveproblems in terms of compatibility and mechanical characteristics.

The inventors have proposed a transparent plastic material whichfunctions to solve such problems and selectively block or reduce lightof a specific wavelength in Japanese Patent Application 05-502109(PCT/JP92/00883; International Open WO93/01233: U.S. Ser. No.08/027,173).

However, the complex compound having the basic structure shown below andcontaining at least one of an aryl group and a heterocyclic group:

(A)n M (wherein n is 3, M denotes Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd,Tb, Dy, Ho, Er, Tm, Yb, or Lu.) has been found to have problems of (1)precipitated when dissolved in polymerizable monomers after decomposedgradually in the state of a crystal, and (2) when the complex compoundis dissolved in a polymerizable monomer and irradiated with light of afluorescent lamp or the like at room temperature, the material has tintsspecific to the individual rare earth elements initially, but tends todiscolor and precipitate with the passage of time.

Therefore, the transparent plastic material of Japanese PatentApplication 05-502109 (PCT/JP0083) using the complex compound has largevariation of color due to a problem in chemical stability of the complexcompound and the occurrence of precipitation.

SUMMARY OF THE INVENTION

With a view to eliminate such problems, a primary object of the presentinvention is to provide a transparent plastic material and opticalarticles comprising the material which do not vary in tints andprecipitation, does not occur have properties of selectively absorbingonly light of a specific wavelength, selectively blocking or reducinglight of wavelengths dazzling to the human eye, and blocking harmfulultraviolet light.

Accordingly the present invention, which attains the above object,provides a transparent plastic material and optical articles comprisingthe material which do not vary in tints and where precipitation does notoccur, and which have high transparency, selective absorption to lightof a specific wavelength, and absorption of harmful ultraviolet light,comprising a polymer obtained by polymerizing a composition comprising(i)at least one polymerizable monomer and (ii)a polymerization initiatoror polymerization catalyst, and containing (iii)a complex compound ofFormula(I).

    A.sub.2 M(OH)(H.sub.2 O)                                   (I)

wherein M denotes Sc, Y, La, Pt, Nd, Pm, Sm, Gd, Dy, Ho, Er, Tm, or Lu;A is a ligand for forming a chelate complex having a structure shownbelow ##STR2## and containing at least one of an aryl group and aheterocyclic group.

The transparent plastic material of a second invention wherein thepolymerizable monomer contains a radical polymerizable group.

The transparent plastic material of a third invention wherein thepolymerizable monomer contains a polyaddition polymerizable group.

The transparent plastic material of a fourth invention wherein thepolymerizable monomer contains a polycondensation polymerizable group.

Optical articles of a fifth invention comprise the transparent plasticmaterial of the first invention.

The optical articles of a sixth invention wherein, in the fifthinvention, the optical articles are eyeglass lenses.

The optical articles of a seventh invention wherein, in the fifthinvention, the optical articles are farsighted eyeglass lenses.

The optical articles of an eighth invention wherein, in the fifthinvention, the optical articles are contact lenses.

The optical articles of a ninth invention wherein, in the fifthinvention, the optical articles are display filters.

The optical articles of a tenth invention wherein, in the fifthinvention, the optical articles are optical apparatus lenses or filters.

The optical articles of an eleventh invention wherein, in the fifthinvention, a thin film layer of the polymer as first invention is formedon a substrate comprising the transparent plastic material.

The optical article of a twelfth invention wherein, in the opticalarticle of the eleventh invention, the substrate comprising thetransparent plastic material is an eyeglass lens, sunglasses, a displayfilter cover, a lighting apparatus cover, an automotive mirror, and anoptical apparatus lens and a filter for cameras.

A production method of an optical article of a thirteenth inventionwherein, in the optical article of the fifth invention, a compositioncomprising one or more polymerizable monomers as described above, apolymerization initiator or catalyst, and a complex compound of Formula(I) is injected into a mold and polymerized.

A production method of an optical article of a fourteenth inventionwherein, in an optical article of the fifth invention, a polymerobtained by polymerizing a composition comprising one or morepolymerizable monomers of the first invention and a polymerizationinitiator or catalyst is melted, mixed with a complex compound ofFormula (I), uniformly dissolved, and solidified as a pellet, the pelletis re-melted using a molding machine such as an injection moldingmachine or the like, and re-solidified in a molding die to obtain anoptical article.

A production method of an optical article of a fifteenth invention ischaracterized in that, in the optical articles of the fifth invention, apolymer obtained by polymerizing a composition comprising one or morepolymerizable monomers of the first invention and a polymerizationinitiator or catalyst is mixed with a complex compound of Formula (I) ina molding machine such as an injection molding machine or the like, andsolidified in a molding die to obtain an optical article.

A production method of an optical article of a sixteenth inventionwherein, in an optical article of the fifth invention, a polymerobtained by polymerizing a composition comprising one or morepolymerizable monomers in the presence of a polymerization initiator orcatalyst is mixed with a complex compound of Formula (I) in a moldingmachine such as an injection molding machine, and solidified in amolding die to obtain an optical article.

The transparent plastic material of a seventeenth invention wherein thepolymer of the second invention comprises a styrene-based transparentplastic material mainly comprising styrene and/or a styrene derivative.

The transparent plastic material of an eighteenth invention wherein thepolymer of the second invention comprises an insocyanurate typetransparent plastic material mainly comprising an isocyanuratederivative having a triazine skeleton and a radical polymerizable group.

The transparent plastic material of a nineteenth invention wherein thepolymer of the second invention comprises a urethane(meth)acrylate typetransparent plastic material mainly comprising urethane(meth)acrylateobtained by reacting an isocyanate group containing compound with ahydroxy group containing compound.

The transparent plastic material of a twentieth invention wherein thepolymer of the second invention comprises a polyester(meth)acrylate typetransparent plastic material mainly comprising a polyester(meth)acrylatehaving a polyester structure in the molecule.

The transparent plastic material of a twenty-first invention wherein thepolymer of the second invention comprises a sulfur-containing(meth)acrylate type transparent plastic material mainly comprising asulfur-containing (meth)acrylate containing sulfur atom in the molecule.

An optical article of a twenty-second invention wherein the opticalarticle comprises a polymer obtained by polymerizing radicalpolymerizable monomers comprising 40 to 60 parts by weight of a(meth)acrylate of Formula (II) containing a sulfur atom in the molecule,10 to 30 parts by weight of an aromatic (meth)acrylate, 10 to 30 partsby weight of an aliphatic (meth)acrylate, and 10 to 30 parts by weightof polyethyleneglycoldimethacrylate in the presence of a radicalpolymerization initiator, and the optical article comprising atransparent plastic material wherein the polymer contains the complexcompound of Formula (I) is an eyeglass lens. ##STR3## wherein R is ahydrogen atom or a methyl group, X is a sulfur atom or an oxygen atom, nis an integer from 0 to 3.

The optical article of a twenty-third invention wherein, in the opticalarticle of the twenty-second invention, M of the complex compound ofFormula (I) is one of Nd, Er, and Ho, and the content is 2 to 15 phmbased on the polymerizable monomers.

The optical article of a twenty-fourth invention wherein, in the opticalarticle of the twenty-third invention, M of the complex compound ofFormula (I) is one of Nd and Er, and the content is 2 to 15 phm based onthe polymerizable monomers.

The optical article of a twenty-fifth invention wherein, in the opticalarticle of the twenty-third invention, M of the complex compound ofFormula (I) is Nd, Er, and Ho, and the content is 2 to 15 phm each basedon the polymerizable monomers.

The Formulae and the present invention are described in detail below.

Specifically, the concept of the plastic material of the presentinvention comprises the polymer comprising the composition of thefollowing i) with a two-coordination compound of the following ii):

i) a "polymer" obtained by polymerizing at least one polymerizablemonomer in the presence of a polymerization initiator or catalyst; and

ii) a "two-coordination complex compound" shown in Formula (I)

    (A).sub.2 M(OH)(H.sub.2 O)                                 (I)

M: Sc, Y, La, Pt, Nd, Pm, Sm, Gd, Dy, Ho, Er, Tm or Lu.

A: A ligand having the structure shown below and forming a chelatecomplex containing at least one of an aryl group and a heterocyclicring. ##STR4##

The present invention solves problems specific to the plastic materialapplied in the international application (PCT/JP92/00883), and thecontents of both applications differ in that the complex compound usedin the above application is a three-coordination complex compound(hereinafter referred to as "three-coordination complex") shown inFormula (III).

    (A).sub.3 M                                                (III)

In contorast the present invention uses a two-coordination complexcompound(hereinafter referred to as "two-coordination complex") shown inFormula (I).

Next, differences between the three-coordination complex of the formerapplication and the two-coordination complex of the present inventionare described.

When optical articles are produced using the plastic material containingthe three-coordination complex, and changes over a long period of timeare being checked, problems have been found in (1) solubility in themonomers, (2) stability after dissolving in a solvent, and (3) stabilityof coloring.

In the course of investigation the causes, of these problems with an eyeon clarification of the stereo structure of the coordination of thecomplex compound, the inventors have found that the problems of thethree-coordination complex are due to steric hindrance, and haveaccomplished the present invention.

However, in the starting stage, synthesis of the complex compound wasthe only method to obtain the formerly disclosed three-coordinationcomplex, synthesis of the two-coordination complex was not considered,and a practical synthetic method was not known.

Therefore, the inventors have conducted studies for a method ofsynthesizing a two-coordination complex for the present invention(details are shown in "Synthesis Examples 1-3" described later.).

Differences in the production method between the three-coordinationcomplex and the two-coordination complex and effects thereof aredescribed in (1) to (6) below. (1) In the synthesis method disclosed inthe previous application, 3 moles of the ligand A always coordinatedwith a trivalent metal M, and a two-coordination complex could not besynthesized. ##STR5##

Therefore, since the presence and synthesis method of a two-coordinationcomplex were unknown when the application on the three-coordinationcomplex was filed, anticipation that the two-coordination complex issuperior to the three-coordination complex in solubility and stabilitywas impossible.

The two-coordination complex has been synthesized in the study forsolving the problems of the three-coordination complex (solubility andstability), and confirmed to be superior to the three-coordinationcomplex for the first time by the present invention.

(2)Production method of two-coordination complex

To a solution dissolving 2 moles of benzoylacetone and 1 mole ofneodymium nitrate in methanol, 4% aqueous ammonia solution is addeddropwise, and reacted at 20° to 25° C. for 1 hour. A blue-violet crystalprecipitates, which is washed with water and dried.

A detailed synthesis method is as shown in "Synthesis Example 1"described later.

The coordination number of the ligands of the complex, for example, whenbenzoylacetone is used as A, that is, which is synthesized, thetwo-coordination complex or the three-coordination complex, depends onthe molar ratio (molar ratio charged) when charging benzoylacetone andneodymium nitrate as shown in Table 1 below.

                  TABLE 1                                                         ______________________________________                                        Benzoylacetone:                                                               Neodymium Nitrate                                                                              Synthesized Complex                                          ______________________________________                                        (Two-coordination complex)2: 1                                                                 Aquahydroxy(1-phenyl-1,3-                                                     dionato)neodymium complex                                                     (1)                                                          (Three-coordination complex)3: 1                                                               TrisBenzoylacetonatoneodymium                                                 complex                                                                       (2)                                                          (Single-coordination complex)1: 1                                                              Diaqua(1-phenyl-1,3-butanedionato)                                            dihydroxyneodymium complex                                                    (3)                                                          ______________________________________                                         (1) (C.sub.6 H.sub.5 COCHCOCH.sub.3).sub.2 Nd(OH)(H.sub.2 O)                  (2) (C.sub.6 H.sub.5 COCHCOCH.sub.3).sub.2 Nd.2H.sub.2 O                      (3) (C.sub.6 H.sub.5 COCHCOCH.sub.3)Nd(OH).sub.2 (H.sub.2 O)             

(3) Next, the analysis method of the two-coordination complex and thethree-coordination method will be briefly described. General analysismethod of complex includes elementary analysis, metal analysis, watercontent, infrared absorption spectrum, DSC (Differential ScanningCalorimeter), and the like.

Elementary analysis

A method for detecting an organic compound or ingredient elements (C, H,O) of an organic compound to determine the contents. Percentages of theindividual ingredient elements are determined, a molecular formula isderived from the result, and the original compound is identified.

Metal analysis

DSC (differential scanning calorimetry)

The sample and a reference substance are placed in the same conditionswhile controlling by heating or cooling, and the energy required formaintaining the temperature difference between the two to zero isrecorded against time or temperature.

An example of the analytical results of the two-coordination complex,three-coordination complex, and single-coordination complex is shown inTable 2 below.

                                      TABLE 2                                     __________________________________________________________________________            Two-Coordination    Single-Coordination                                       Complex   Three-Coordination                                                                      Complex                                                   Aquahydroxy(1-                                                                          Complex   Diaqua(1-phenyl-1,                                        phenyl-1, 3-                                                                            Trisbenzoyl                                                                             3-butanedionato)                                          butanedionato)                                                                          acetonatoneodymium                                                                      dihydroxyneodymium                                        neodymium complex                                                                       complex   complex                                           __________________________________________________________________________    Elementary                                                                    analysis                                                                      (Calculated)                                                                        C 47.88%    54.28%    31.98%                                                  H 4.22      4.70      4.02                                              (Measured)                                                                          C 47.94     54.34     31.56                                                   H 3.90      4.58      4.30                                              Metal analysis                                                                (Nd)                                                                          (Calculated)                                                                          28.8      21.7      40.5                                              (Measured)                                                                            30.0      22.1      38.4                                              Water content                                                                 (Calculated)                                                                          3.6       5.4       9.5                                               (Measured)                                                                            4.1       4.58      10.7                                              DSC     170° C.                                                                          180° C.                                                                          183° C.                                    (Melting point)                                                               Infrared                                                                              FIG. 15   FIG. 17   --                                                absorption                                                                    spectrum                                                                      Visible FIG. 16   FIG. 18   Insoluble in                                      ultraviolet                 toluene                                           absorption                                                                    spectrum                                                                      (2% toluene                                                                   solution)                                                                     __________________________________________________________________________

(4) The basis of the chemical stability of the two-coordination complexis be described below.

When the ligand coordinating the metal atom has a bulky structure likebenzoylacetone, the three-coordination complex is in an unstable statein view of energy due to a steric hindrance. In this case, in the statewhere the complex is dissolved in a solvent or monomer, the degree offreedom increases, and it changes to a low entropy state.

Therefore, the three-coordination complex changes to a state which isstable as to energy,that means,it decomposes.

FIG. 19 simulates a structure where a two-coordination complex(aquahydroxy(1-phenyl-1,3-butanedionato)neodymium) is the most stable asto energy.

As shown in FIG. 19, in the two-coordination complex, two units of bulkybenzoylacetone coordinate to a metal M (Nd atom) symmetrically with thephenyl groups at the outside, and OH and H₂ O coordinate the remainingconformers. The structure of the two-coordination complex is much lessaffected by steric hindrance compared with the three-coordinationcomplex, and is thus stable in energy.

Therefore, since the two-coordination complex takes a stable state evenwhen dissolved in a solvent or monomer with a high degree of freedom, nodecomposition nor change in color takes place.

(5)Stability test

Next, the improved chemical stability when dissolved in a polymerizablemonomer is described.

Detailed test examples are described later (Test Examples 1 to 8).

In the present invention, improvement of chemical stability in the statewhen dissolved in a polymerizable monomer means the followingconditions.

(1) No change in color occurs over time.

(2) No precipitation takes place over time by decomposition of thecomplex.

As a result, (1) the two-coordination complex can always provide thesame color, and (2) when the two-coordination complex is dissolved in amonomer, the solution can be stored for a long period of time.

That is, since the raw materials can be previously mixed, limitation ofthe molding process time can be reduced, and raw materials used formolding for a week can be mixed in a single mass, and efficiency of thework can be improved, leading to a cost reduction.

In the present invention, it is preferable to use the two-coordinationcomplex in a pure state, but a small amount of a three-coordinationcomplex can be present in view of the solubility and stability,as willbe described later.

(6) Color stability of the transparent plastic material obtained usingthe two-coordination complex is shown below

An achromatic color such as gray can be obtained using conventionalthree-coordination complexes depending on the combination of complexcompounds.

However, the three-coordination complex has a problem of stability afterdissolution in a monomer, that is, a stable achromatic color cannot beobtained due to a change in color time. The material obtained with thetwo-coordination complex, which is described in the present invention,has a good stability and solves the above problem.

Combinations of two-coordination complexes and resulting colors areshown in Table 3.

                  TABLE 3                                                         ______________________________________                                                       Absorption                                                     Ratio of Complex                                                                             Wavelength of                                                                              Color of                                          BANd  BAEr     BAHo    Molding (lens)                                                                           Molding                                     ______________________________________                                        50    50       --      510-530    Gray                                                               570-590                                                65    35       --      510-530    Blue-violet                                                        570-590                                                35    65       --      510-530    Violet-dark blue                                                   570-590                                                65    --       35      440-460    Blue-green                                                         570-590                                                35    --       65      440-460    Yellow-green                                                       570-590                                                --    50       50      440-460    Green                                                              570-590                                                --    50       50      440-460    Brown                                                              510-530                                                ______________________________________                                    

(7) As described above, differences between the use of thetwo-coordination complex and the use of the prior art ofthree-coordination complex are summarized as follows.

1) Solubility Test

The two-coordination complex is readily soluble in monomers, and thethree-coordination complex has inferior solubility.

As a result, the content of the two-coordination complex can be greatlyincreased.

2) Stability Test

i) When the two complexes are dissolved individually in a solvent, thereare differences in changes over time.

As a result, the two-coordination complex is superior in handling (forexample, can be stored for a long time dissolved in a solvent, and canbe dealt with when the machine stops accidentally), and in advantageouscompared with the three-coordination complex.

ii) There are changes in coloring.

As a result, the two-coordination complex always provides a material ofthe consistent color.

iii) Combination of the two-coordination complex with thethree-coordination complex

No considerable difference is noted in changes over time even when asmall amount of the three-coordination complex is mixed with thetwo-coordination complex, but preferably the total amount is thetwo-coordination complex.

Therefore, even if a small amount of the three-coordination complex isadded, the resulting mixture is usable in view of solubility andstability.

Specific examples of the complex compound of Formula (I) of the presentinvention are shown below:

    (A).sub.2 M(OH)(H.sub.2 O )                                (I) ##STR6##

The complex compound of Formula (I-1) is shown below as an example ofthe complex compound of Formula (I) of the present invention.

In the following chemical structure, when M is Nd the steric structureis as shown in FIG. 19. ##STR7##

The complex compound of Formula (I) is an essential ingredient to endowthe transparent plastic material with a selective absorption function tolight of a specific wavelength, and is preferably present in an amountof 0.1 to 20% by weight. If the amount of the complex compound is lessthan 0.1% by weight, the above effect is low, and if it exceeds 20% byweight, the physical characteristics of the resulting plastic materialtend to be deteriorated, which is not preferable.

Further, the complex compound differs in the wavelength of sharpabsorption depending on the type of rare earth element M, and thetransparent plastic material containing the complex compound and opticalarticles comprising the same have properties to selectively block orreduce only light of specific wavelengths. The transparent plasticmaterial containing the complex compound and optical articles comprisingthe same have properties to selectively block or reduce only light ofwavelengths which largely affect the human eye, and properties toselectively block or reduce only light of wavelengths which are dazzlingto the human eye. When M is Nd (neodymium), the material has a sharpabsorption in the vicinity of 570 to 590 nm and, when M is Pm(promethium), it has a sharp absorption in the vicinity of 560 to 580nm, which agrees with the wavelength range of high specific luminosityfactor in light adaptation sight, therefore they provide the transparentplastic material with a glare-proof function. Er (erbium) gives a sharpabsorption in the vicinity of 510 to 530 nm, and Ho (holmium) gives asharp absorption in the vicinity of 440 to 460 nm, which provides endowthe material with a glare-proof function in dark adaptation sight.Therefore, since the wavelength range of selective absorption differsdepending on the type of rare earth element in the complex compound, itcan be selectively utilized according to the purpose of application.Further, it is also possible to use a plurality of complex compoundswith different absorption wavelength ranges in order to enhance theglare-proof function. Since the complex compound of the presentinvention contains an aromatic ring or a heterocyclic ring in the ligandas shown in the above Formula (1-1)˜(1-7), ultraviolet light of lessthan 400 nm in wavelength is absorbed. Therefore, the transparentplastic material containing the complex compound and optical articlescomprising the same have properties to block ultraviolet light which isharmful to the human eye. This is effective for preventing cataracts,prevention of electrical ultraviolet light in a skiing ground, andprevention of adverse effects of ultraviolet light on sugi pollinosis(allergic conjunctivitis), particularly suitable for use in opticalarticles for sight correction such as eyeglass lenses and contactlenses. Therefore, the transparent plastic material of the presentinvention is not required to be combined with ultraviolet absorberswhich are generally used, or it is possible to reduce the amounts ofsuch additives.

The complex compound of Formula (I) used in the present invention ishydrophobic lipophilic, and thus has better compatibility with typicalpolymerizable monomers forming the transparent plastic material comparedwith conventional rare earth compounds. In particular, it has superiorcompatibility with hydrophobic polymerizable monomers. Further, when thecomplex compound is dissolved in a polymerizable monomer, it is tinted acolor specific to the individual rare earth element, it does notdiscolor over time under irradiation with light of a fluorescent lamp orthe like at room temperature, it does not cause precipitation, and itexhibits good chemical stability.

Further, the polymer containing the complex compound has a hightransparency and superior selective absorptivity to light of a specificwavelength due to a rare earth element, and absorbs harmful ultravioletlight, without variation in tint and occurrence of precipitation. Thepolymer, since the complex compound of Formula (I) has goodcompatibility with hydrophobic polymerizable monomers, can have animproved water resistance without using a water-soluble metal salt and ahydrophilic polymerizable monomer, the dimensional stability is improvedsince there is no problem of increasing water absorptivity, and there isno problem of cracking when a deposition film is provided on the surfaceof the polymer. Further, since the complex compound of Formula (I) hasan ultraviolet absorbing function, it is not required to add anultraviolet absorber separately, and even if an ultraviolet absorber isto be added, the amount can be reduced to a very small quantity, whichcan solve the problem of compatibility such as precipitation of theultraviolet absorber, and prevent deterioration of mechanicalcharacteristics of the polymer.

Of the above-described complex compounds of Formula (I), those ofFormulae (1-1-a) to (1-4-d) have particularly good compatibility withpolymerizable monomers. ##STR8##

Of the above complex compounds, use of the following compounds isparticularly preferable. ##STR9##

The content of the above two-coordination complex compound in thepolymerizable monomer is 1 to 20 phm, more preferably 2 to 15 phm.

If the content is less than I phm, the resulting optical articles do nothave any glare-proof effect, and even if the content exceeds 20 phm,further addition is unnecessary since 100% of a specific wavelength iscut off.

If the amount is within the above content, using two-coordinationcomplex compounds containing, for example, Nd, Er, and Ho as rare earthelements in appropriate amounts, the molding can be endowed with adesired color.

The two-coordination complex compound of Formula (I) is synthesized bythe following method. Specifically, 1 mole of rare earth metal nitrateand 2 mole of 1,3-diketone are dissolved in methanol, 4% aqueous ammoniasolution is added dropwise, reacted at 20° to 25° C. after the dropping,the precipitated crystal is filtered, and washed with water to obtainthe complex compound of Formula (I).

The polymerizable monomer in the present invention means a compoundwhich can produce polymers, and the formation reaction of the polymerincludes radical polymerization, ionic polymerization, coordinationpolymerization, ring-opening polymerization, polyaddition,polycondensation, addition condensation, and the like.

The polymerizable monomer in the present invention can be radicalpolymerizable compounds which are generally used, having at least oneunsaturated hydrocarabon group such as vinyl group, allyl group, acrylor methacryl group, vinylidene group, vinylene group, or the like in themolecule. Specifically, they include styrene derivatives such asstyrene, methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene,bromostyrene, p-chloromethylstyrene, and divinylbenzene; monofunctionalacrylic esters such as acrylic acid, methyl acrylate, ethyl acrylate,n-butyl acrylate, butoxyethyl acrylate, benzyl acrylate, phenylacrylate, phenoxyethyl acrylate, cyclohexyl acrylate, dicyclopentanylacrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate,tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethylacrylate, 2-hydroxypropyl acrylate, 2-acryloyloxyethyl succinic acid,and 2-acryloyloxyethyl phthalic acid,caprolactone acrylate,glycidylacrylate: monofunctional methacrylic esters such as methacrylic acid,methyl methacrylate ethyl methacrylate, n-butyl methacrylate,2-ethylhexyl methacrylate, butoxymethyl methacrylate, benzylmethacrylate, phenyl methacrylate, phenoxyethyl methacrylate, cyclohexylmethacrylate, dicyclopentanyl methacrylate, dicyclopentenylmethacrylate, dicyclopentenyloxyethyl methacrylate, tetrahydrofurfurylmethacrylate, isobornyl inethacrylate, 2-hydroxyethyl methacrylate,2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and glycerolmethacrylate, 2-methacryloyloxyethyl succinic acid,2-methacryloyloxyethyl phthalic acid, caprolactone methacrylate,glycidyl methacrylate; allyl compounds such as allylbenzene,allyl-3-cyclohexane propionate, 1-allyl-3,4-dimethoxybenzene,allylphenoxy acetate, allylphenyl acetate, allylcyclohexane, and allylpolycarboxylate; fumaric acid, maleic acid, itaconic acid, and theiresters, acrylonitrile, methacrylonitrile, maleic anhydride,N-substituted maleimide, and cyclic olefins.

Furthermore, in order to enhance the degree of cross-linking,multifunctional monomers such as ethyleneglycol diacrylate,diethyleneglycol diacrylate, triethyleneglycol diacrylate,tetraethyleneglycol diacrylate, polyethyleneglycol diacrylate, allylacrylate, bis(acryloxyethyl)hydroxyethyl isocyanurate,bis(acryloxyneopentylglycol)adipate, 1,3-butyleneglycol diacrylate,1,6-hexanediol diacrylate, neopentylglycol diacrylate, propyleneglycoldiacrylate, polypropyleneglycol diacrylate,2-hydroxy-1,3-diacryloxypropane, 2,2-bis 4-(acroyloxy)phenyl!propane,2,2-bis 4-(acroyloxyethoxy)phenyl!propane, 2,2-bis4-(acryloxyethoxy-diethoxy)phenyl!propane, 2,2-bis4-(acryloxyethoxy-polyethoxy)phenyl!propane, neopentylglycoldiacrylatehydroxypivalate, 1,4-butanediol diacrylate, dicyclopentanyldiacrylate,dipentaerythritol hexaacrylate,dipentaerythritolmonohydroxypentaacrylate, di-trimethylpropanetetraacrylate, pentaerythritol triacrylate, tetrabromobisphenol Adiacrylate, triglycerol diacrylate, trimethylpropane triacrylate,tris(acryloxyethyl)isocyanurate, ethyleneglycol dimethacrylate,diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate,tetraethyleneglycol dimethacrylate, polyethyleneglycol dimethacrylate,propyleneglycol dimethacrylate, polypropyleneglycol dimethacrylate,1,3-butyleneglycol dimethacrylate, 1,4-butanediol dimethacrylate,1,6-hexanediol dimethacrylate, neopentylglycol dimethacrylate,2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis4-(methacryloxy)phenyl!propane, 2,2-bis4-(methacryloxyethoxy-ethoxy)phenyl!propane, 2,2-bis4-(methacryloxyethoxy-diethoxy)phenyl!propane, 2,2-bis4-(methacyloxyethoxy-polyethoxy)phenyl!propane, tetrabromobisphenol Adimethacrylate, dicyclopentanyl dimethacrylate, dipentaerythritolhexamethacrylate, glycerol dimethacrylate, neopentylglycoldimethacrylatehydroxypivalate, dipentaerythritol monohydroxypentamethacrylate,ditrimethylolpropane tetramethacrylate, pentaerythritol trimethacrylate,pentaerythritol tetramethacrylate, triglycerol dimethacrylate,trimethylpropane trimethacrylate, tris(methacryloxyethyl)isocyanurate,allylmethacrylate, divinylbenzene, diallylphthalate,diallylterephthalate, diallylisophthalate, and diethyleneglycolbisallylcarbonate can be used. However, when unsaturated carboxylicacids such as methacrylic acid, acrylic acid, 2-hydroxyethylmethacrylate, 2-hydroxyethyl acrylate, 2-hydroxylpropyl methacrylate,2-hydroxypropyl acrylate, 2-acryloyloxyethyl succinic acid,2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid,2-methacryloyloxyethyl phthalic acid, glycidyl acrylate, glycidylmethacrylate,glycerol methacrylate, fumaric acid, maleic acid, anditaconic acid; or hydrophilic polymerizable monomers such asdiethyleneglycol diacrylate, diethyleneglycol dimethacrylate,triethyleneglycol diacrylate, triethyleneglycol dimethacrylate,polyethyleneglycol diacrylate, polyethyleneglycol dimethacrylate,polypropyleneglycol diacrylate, polypropyleneglycol dimethacrylate, andglycerol dimethacrylate are used, it is required to use these monomersonly in amounts having no effects on the water absorption properties ofthe resulting polymer.

The amount of the complex compound of Formula (I) to be dissolved inthese polymerizable monomers may vary. Therefore, the amount of thecomplex compound added must be appropriately determined within the rangewhere deterioration in mechanical strength of the resulting plasticmaterial is very small, transparency is maintained, and properties toblock or reduce light of a specific wavelength due to the selectiveabsorptivity of the specific wavelength are achieved.

These polymerizable monomers may be used alone or as combinations of twoor more types. Furthermore, they may be used in combination witholigomers or macromers such as those of polyester (meth)acrylate,urethane (meth)acrylate, and epoxy (meth)acrylate.

The polymer of the present invention comprising these polymerizablemonomers can be obtained by thermal polymerization orphotopolymerization by ultraviolet light, electromagnetic wavepolymerization using electronic wave, or radiation polymerization usingradiation.

As a thermal polymerization initiator, peroxy esters such ast-butylperoxyneodecanoate, t-butylperoxypivalate,t-butylperoxyisobutyrate, t-butylperoxyacetate, cumylperoxyneodecanoate,t-butylperoxyoctoate, t-butylperoxyisopropylcarbonate, cumylperoxyoctoate, t-hexylperoxyneodecanoate, t-hexylperoxypivalate,t-butylperoxyneohexanoate; peroxyketals such as1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane,2,2-bis(t-butylperoxy)butane; diacrylperoxides such as acetylperoxide,isobutylylperoxide, octanoylperoxide, lauroylperoxide, benzoylperoxide,and m-toluoylperoxide; organic peroxide initiators such asdiisopropylperoxy dicarbonate, and di-n-propylperoxy dicarbonate; azocompound initiators such as 2,2'-azobisisobutyronitrile,1,1'-azobis(cyclohexane-1-carbonitrile),2,2'-azobis(2-methylbutyronitrile),2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate,and 2,2'-azobis(2,4,4-trimethylpentane); or redox type initiators can beused, preferably in an amount of 0.01 to 5% by weight. As aphotopolymerization initiator, acetophenone type initiators such asdiethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,1-oxy(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one,1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one,4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone, and1-hydroxycyclohexylphenylketone; benzoin type initiators such asbenzoin, benzoinmethylether, benzoinethylether, benzoinisopropyl ether,benzoinisobutyl ether, and benzyldimethylketal; benzophenone typeinitiators such as benzophenone, benzoylbenzoic acid, methylbenzoylbenzoate, 4-phenylbenzophenone, and hydroxybenzophenone; oracrylphosphineoxide type initiators such as2,4,6-trimethylbenzoyldiphenylphosphineoxide,2,6-dimethylbenzoyldiphenylphosphineoxide, andbenzoyldiethoxyphosphineoxide can be used, preferably in an amount of0.001 to 5% by weight. Further, dicarbonyl type initiators such asbenzil, camphor-quinone, anthraquinone, and acenaphthene: thioxansontype initiators such as 2-methylthioxanson, and 2,4-diethylthixanson; oracylphosphineoxide type initiators initiators such as2,4,6-trimethylbenzoyldiphenylphosphineoxide,2,6-dimethylbenzoyldiphenylphospbeneoxide, andbenzoyldiethoxyphosphineoxide can also be used as visible light curingphotopolymerization intiators, preferably in an amount of 0.001 to 5% byweight. Still further, the thermal polymerization initiators and thephotopolymerization initiators can also be used in combination.

The mixture comprising the complex compound of Formula (I), the abovepolymerizable monomer, and the polymerization initiator can be mixed, asnecessary, with small amounts of a thermal stabilizer, an antioxidant, aphotostabilizer, a release agent, a chain transfer agent, apolymerization controller, and the like.

Plastic materials which have good compatibility with the complexcompound of Formula (I) and can provide highly transparent plasticmaterials include a styrene based transparent plastic material, anisocyanurate type transparent plastic material, a urethane(meth)acrylate type transparent plastic material, a polyester(meth)acrylate type transparent plastic material, and asulfur-containing (meth)acrylate type transparent plastic material.

Here, the styrene type transparent plastic material means a polymermainly comprising styrene and/or a styrene derivative, for example, apolymer mainly comprising styrene or styrene derivative obtained bypolymerizing a mixture of at least one polymerizable monomer of styreneor a styrene derivative of Formula (2-1), at least one polymerizablemonomer of Formula (2-2), and as necessary, at least one radicalpolymerizable monomer.

The isocyanurate type transparent plastic material means a polymermainly comprising an isocyanurate derivative having a triazine skeletonand a radical polymerizing group in the molecule, for example, a polymermainly comprising an isocyanurate derivative obtained by polymerizing amixture of a trifunctional polymerizable monomer of Formula (2-3) havinga triazine skeleton and a radical polymerizing group in the molecule anda polymerizable monomer which can copolymerize with the above component.

The urethane (meth)acrylate type transparent plastic material means apolymer mainly comprising ; urethane (meth)acrylate obtained by reactingan isocyanurate group containing compound with a hydroxy groupcontaining compound, for example, a polymer mainly comprising a urethane(meth)acrylate obtained by polymerizing a mixture of a urethane(meth)acrylate obtained by reacting a compound of Formula (2-4) with ahydroxy group containing compound, and a radical polymerizable monomeror oligomer.

The polyester (meth)acrylate type transparent plastic material means apolymer mainly comprising a polyester (meth)acrylate having a polyesterstructure in the molecule, for example, a polymer mainly comprising apolyester (meth)acrylate obtained by polymerizing a mixture of at leastone polymerizable monomer of Formula (2-5) and a radical polymerizablemonomer or oligomer, or a polymer mainly comprising a polyester(meth)acrylate of Formula (2-6) obtained by polymerizing a mixture of acompound of Formula (2-6) and ethyleneglycol dimethacrylate compound andan aromatic vinyl compound.

The sulfur containing (meth)acrylate type transparent plastic materialmeans a polymer mainly comprising a (meth)acrylate containing a sulfuratom in the molecule, for example, a polymer mainly comprising a sulfurcontaining (meth)acrylate obtained by polymerizing a mixture of a thiol(meth)acrylate of Formula (2-8) and a radical polymerizable monomer.##STR10##

As the polymerizable monomer in the present invention, a polyadditionpolymerizable compound can be used. A polyaddition reactive group meansa group which is possible to undergo addition reaction, and typicalexamples thereof include an isocyanate group (--NCO), an isothiocyanategroup (--NCS), and groups reactable with the reactive group include ahydroxy group, an amino group, a inercapto group, and a carboxyl group.That is, the polymerizable monomer which can form a polymer in thepresent invention comprises a compound having at least two isocyanate orisothiocyanate groups in the molecule as shown in the following Formulae(4-a) to (4-b), and a compound having either of at least two hydroxygroups, amino groups, mercapto groups, or carboxyl groups as shown inFormulae (4-c) to (4-f), wherein m, m' indicate an integer of 2 or more.

    ______________________________________                                               R-(NCO) m       (4-a)                                                         R-(NCS) m       (4-b)                                                         R'-(OH) m'      (4-c)                                                         R'-(NH2) m'     (4-d)                                                         R'-(SH) m'      (4-e)                                                         R'-(COOH) m'    (4-f)                                                  ______________________________________                                    

Here, typical examples of isocyanate reactions are shown in Formulae(5-1), (5-2), (6-1) to (6-6). ##STR11##

Further, typical examples of isothiocyanate reactions are shown inFormulae (7-1) to (7-8). ##STR12##

Specific examples of the compound of Formula (4-a) include hexamethylenediisocyanate, 2,4,4-trimethylhexamethylene diisocyanate,1,3,6-hexamethylene triisocyanate, xylylene diisocyanate, isophoronediisocyanate, dicyclohexylmethane diisocyanate, cyclohexanediisocyanate, tolylene diisocyanate, toluidine diisocyanate,4,4'-diphenylmethane diisocyanate, thiodiethyl diisocyanate,thiodipropyl diisocyanate, diphenylsulfide-2,4'-diisocyanate, and2,2'-dimethyldiphenyldisulfide-5,5'-diisocyanate. Practical examples ofthe compound of Formula (4-b) include 1,2-diisothiocynateethane,1,3-diisothiocynatepropane, 1,2-diisothiocyanatebenzene, and1,1'-methylenebis(4-isothiocyanate-3-methylbenzene).

Further, examples of the compound of Formulae (4-c) to (4-f) includepolyetherpolyol, polytetramethyleneetherglycol, alkyleneoxidecopolymerized polyol, epoxy resin modified polyol, lactone typepolyesterpolyol, condensation type polyesterpolyol, polycarbonatediol,acrylic polyol, polybutadienepolyol, phosphorus-containing polyol,halogen-containing polyol, polyetherpolyamine,polytetramethyleneetherdiamine, alkyleneoxide-copolymerized polyamine,epoxy resin modified polyamine, condensation type polyesterpolyamine,polycarbonatediamine, acrylic polyamine, polybutadienepolyamine,phosphorus-containing polyamine, halogen-containing polyamine,polyetherpolyol, polytetramethyleneetherdithiol,alkyleneoxide-copolymerized polythiol, epoxy resin modified polythiol,lactone type polyesterpolythiol, condensation type polyester polythiol,polycarbonatedithiol, acrylic polythiol, polybutadienepolythiol,phosphorus-containing polythiol, halogen-containing polythiol, and thelike. In these compounds, it is preferable to determine the molecularstructure of the basic skeleton in order to obtain properties dependingon the use of the resulting polymer. The polymer of the presentinvention can be obtained by a polyaddition reaction. That is, ingeneral, under the presence of a polymerization catalyst, apolymerizable monomer of Formulae (4-a) to (4-b) and a polymerizablemonomer of Formulae (4-c) to (4-f) are mixed, and heated to obtain apolymer. As the polymerization catalyst, amine catalysts includingmonoamines such as triethylainine, and N,N-dimethylcyclohexylamine:diamines such as N,N,N',N'-tetramethylethylenediamine,N,N,N',N'-tetramethylpropane-1,3-diamine; triamines such asN,N,N',N'-pentamethyldiethylenetriamine,N,N,N',N'-pentamethyldipropylenetriamine, and tetramethylguanidine;cyclic amines such as triethylenediamine, N,N'-dimethylpiperazine,N-methyl-N'-(2-dimethylamino)ethylpiperazine, N-methylmonopholine,N-(N',N'-dimethylaminoethyl)morpholine, and 1,2-dimethylimidazole;alcoholamines such as dimethylaminoethanol, dimethylaminoethoxyethanol,N,N,N'-trimethylaminoethylethanolamine,N-methyl-N'-(2-hydroxyethyl)piperazine, N-(2-hydroxyethyl)monopholine:etheramines such as bis(2-dimethylaminoethyl)ether, andethyleneglycolbis(3-dimethyl)aminopropylether; and organic metalcatalysts such as dibutyltindilaurate, dibutyltindiacetate,dibutyltinmercaptide, dibutyltinthiocarboxylate, dibutyltindimaleate,dioctyltinmercaptide, dioctyltinthiocarboxylate, phenylinercurypropionicacid salt, and lead octenate. These polymerization catalysts can be usedalone or in combination of two or more types.

The amount of the complex compound of Formula (I) to be dissolved inthese polymerizable monomers may vary, but must be appropriatelydetermined within the range where the transparency is maintained, andthe properties to block or reduce light of a specific wavelength due tothe selective absorptivity of the specific wavelength are achieved.Further, the mixture of the complex compound of Formula (I), thepolyaddition polymerizable monomer, and the polymerization catalyst canbe mixed, as necessary, with a substance such as an optical stabilizer,an ultraviolet absorber, an antioxidant, or an internal release agent.

Of the above-described polyaddition polymerizable monomers, those whichhave good compatibility with the complex compound of Formula (I), andcan provide a transparent plastic material which has high transparencyand a relatively high refractive index (1.60 to 1.75) include asulfur-containing urethane resin type transparent plastic materialobtained by reacting a mercapto compound of Formula (8) and at least oneester compound selected from the group consisting of a polyiocyanatecompound, a polyisothiocyanate compound, and an isothiocyanate compoundhaving an isocyanate group in the presence of a polymerization catalyst,as disclosed in Japanese OPI 02-270859/1990. ##STR13##

Still further, as a polymerizable monomer in the present invention, apolycondensation polymerizable compound can be used. A polycondensationreactive group is a functional group which can undergo condensationreaction, including a carboxyl group (--COOH), a hydroxy group (OH), anamino group (NH3), an alkoxy group (--OR: where R is an alkyl group),and the like. That is, a polymerizable monomer which can produce apolymer comprises a compound having at least two carboxyl groups in themolecule as shown in Formula (9-a), and a compound having at least twohydroxyl groups, amino groups, or alkoxy groups in the molecule as shownin Formulae (9-b), (9-c), (9-d) and the like. In the Formulae, m and m'are integers of 2 or more.

    R'--(COOH)m                                                (9-a)

    R'--(OH)m'                                                 (9-b)

    R'--(NH2)m'                                                (9-c)

    R'--(OR)m'                                                 (9-d)

    R'--(COOR)m                                                (9-e)

Examples of typical polycondesation reaction are shown in Formulae(10-a) to (10-d). ##STR14##

The compound of Formula (9-a) specifically includes dicarboxylic acidssuch as terephthalic acid, adipic acid, and the like. The compound ofFormula (9-b) specifically includes diols such as ethyleneglycol,propyleneglycol, and the like. The compound of Formula (9-c)specifically includes diamines such as hexamethylenediainine and thelike. The compound of Formula (9-d) specifically includes silanecompounds such as 3-glycidoxypropyltrimethoxysilane,3-methacryloxydipropyltrimethoxysilane, and the like. The compound ofFormula (9-e) specifically includes dicarboxylic acid diesters such asdimethyl terephthalate and the like. The polymer of the presentinvention is generally obtained by heating or heating in the presence ofa catalyst.

The amount of the complex compound of Formula (I) to be dissolved inthese polymerizable monomers is may vary, but must be appropriatelydetermined within the range where the transparency is maintained, andthe properties to block or reduce light of a specific wavelength due tothe selective absorptivity of the specific wavelength are achieved.Further, the mixture of the complex compound of Formula (I), thepolycondensation polymerizable monomer, and the polymerization catalystcan be mixed, as necessary, with a substance such as an opticalstabilizer, an ultraviolet absorber, an antioxidant, or an internalrelease agent.

The polymer in the present invention indicates a compound produced by apolymerization reaction such as radical polymerization, ionicpolymerization, coordination polymerization, ring-openingpolymerization, polyaddition polycondensation, and the like.

Since the two-coordination complex compound of Formula (I) used in thepresent invention is lipophilic, it has superior compatibility withthermoplastic polymers as compared with conventional rare earthcompounds. Polymers (thermoplastic resins) with transparency andthermoplasticity include polymethylmethacrylate, polycarbonate,polystyrene, polyvinylchloride, MS resin (styrene-methylmethacrylatecopolymer), AS resin (acrylonitrile-styrene copolymer),polycyclohexylmethacrylate, poly-4-methylpentene-1, amorphous polyamide,amorphous polyolefin, transparent fluororesin, fluorinated polyimide,transparent polybutyleneterephthalate, polyacrylate, polysulfone,polyethersulfone, and the like. The transparent plastic materialcomprising the above polymers can be obtained by mixing the moltenpolymer with the complex compound of Formula (I), followed bysolidification.

The transparent plastic material of the present invention can be used inoptical articles including optical apparatus lenses and filters such aseyeglass lenses, contact lenses, intraocular lenses, sunglasses, displayfilter covers, lighting apparatus covers, automotive mirrors, and thelike. Further, the material can also be used as a hard coat for eyeglasslenses and optical apparatus lenses.

The optical articles comprising the transparent plastic material of thepresent invention can be obtained by cast molding a compositioncomprising one or more polymerizable monomers, a polymerizationinitiator or catalyst, and the complex compound of Formula (I) used inthe present invention. Specifically, in eyeglass lenses, a mixturecomprising one or more polymerizable monomers, a polymerizationinitiator or catalyst, and the complex compound of Formula (I) used inthe present invention is injected into a mold comprising a glass-mademold and a gasket of a soft resin such as ethylene-vinyl acetatecopolymer to be cast molded (cast polymerized) to obtain eyeglass lensescomprising the transparent plastic material of the present invention.Similarly, optical articles such as contact lenses, intraocular lenses,sunglasses, display filters, and optical apparatus lenses can also beobtained by cast molding.

Alternatively, the optical articles comprising the transparent plasticmaterial of the present invention can be obtained by a method in which apolymer obtained by polymerizing a composition comprising one or morepolymerizable monomers and a polymerization initiator or catalyst ismelted, mixed with the complex compound of Formula (I) to be dissolvedand solidified to obtain a pellet, the pellet is re-melted using amolding machine such as an injection molding machine, and solidified ina mold. Further, the optical articles comprising the transparent plasticmaterial of the present invention can also be obtained by mixing apolymer obtained by polymerizing a composition comprising one or morepolymerizable monomers and a polymerization initiator or catalyst withthe complex compound of Formula (I) used in the present invention in amolding machine such as an injection molding machine, and solidifying ina mold. Still further, the optical articles comprising the transparentplastic material of the present invention can also be obtained bymelting a polymer obtained by polymerizing a mixture comprising one ormore polymerizable monomers, a polymerization initiator or catalyst, andthe complex compound of Formula (I) used in the present invention usinga molding machine such as an injection molding machine, and solidifyingin a mold. Specifically, optical articles such as display filter covers,lighting apparatus covers, automotive mirrors, sunglasses, and opticalapparatus lenses and filters such as for cameras can be obtained by theabove method.

The optical articles comprising the transparent plastic material of thepresent invention can be obtained by forming a thin film layer of apolymer obtained by polymerizing a composition comprising one or morepolymerizable monomers, a polymerization initiator or catalyst, and thecomplex compound of Formula (I) used in the present invention on asubstrate comprising a transparent plastic material. Specifically, theoptical articles such as eyeglass lenses, sunglasses, display filtercovers, lighting apparatus covers, automotive mirrors, optical apparatuslenses and filters for cameras, and the like can be obtained by theabove method.

Here farsighted eyeglass lenses indicate single focus convex lenses,double focus lenses, progressive multiple focus lenses, and the like. Asto farsighted eyeglass lenses of the present invention, single focusconvex lenses can be obtained by the above cast molding. Progressivemultiple focus lenses can be obtained by injecting a mixture comprisingone or more polymerizable monomers and a polymerization initiator orcatalyst with the complex compound of Formula (I) used in the presentinvention in a mold formed of two glass molds for progressive multiplefocus lens and a gasket comprising a flexible resin such asethylene-vinyl acetate copolymer to be cast molded (cast polymerized).

Since contact lenses are medical supplies contacting directly with thecornea, it is preferable to use a substance which is readily soluble inthe polymerizable monomer as is the complex compound used in the presentinvention. Further, as the polymerizable monomer, use of an acrylicester or a methacrylic ester is particularly preferable. For contactlenses, it is preferable that the polymerizable monomer is injected in aglass tube or a polypropylene or polytetrafluoroethylene tube or asheet-formed gap and polymerized by heating, or photopolymerized byirradiation with ultraviolet light. If a deflection occurs in thepolymer due to polymerization shrinkage or polymerization heat afterpolymerization, it can be eliminated by heat annealing.

ACTION

Eyeglass lenses comprising the transparent plastic material of thepresent invention have properties to selectively block or reduce lightof a wavelength largely affecting the human eye, and selectively blockor reduce only light of a wavelength which is dazzling to the human eye.For example, the complex compound of Formula (I) used in the presentinvention has a sharp absorption in the vicinity of 570 to 590 nm when Mis neodymium and 560 to 580 nm when M is prometium, which is in linewith the wavelength range of relatively high sensitivity in lightadaptation sight, and provides eyeglass lenses of the present inventionwith glare-proof properties in light adaptation sight. For erbium andhoronium, a sharp absorption is in the vicinity of 510 to 530 nm, 440 to460 nm, which provides glare-proof properties in the dark adaptationsight. Therefore, since the wavelength of selective absorption differsdepending on the type of rare earth element in the complex compound, itis possible to select a suitable type according to the application.Further, it is possible to enhance the glare-proof function by using aplurality of complex compounds with different absorption wavelengthranges. Since, in the compound used in the present invention, the ligandcontains an aromatic ring or a heterocyclic ring, it can absorbultraviolet light of less than 400 nm in wavelength. Therefore, since ithas a function to block ultraviolet light which is harmful to the humaneye, it is effective to prevent occurrence of cataracts, preventelectrical ophthalmia generated by a welding light or exposure to strongultraviolet light in a skiing area, and prevention of adverse effects ofultraviolet light on sugi pollinosis (allergic conjunctivitis). Furtheras for, environmental factors of eye fatigue include light from atelevision and displays, and other strong light, in particular, light ofa wavelength range of high sight sensitivity and ultraviolet light,eyeglass lenses comprising the transparent plastic material of thepresent invention can block or reduce such strong light and also blockultraviolet light, and eye fatigue can be reduced or prevented. Contactlenses and display filters comprising the transparent plastic materialof the present invention have similar functions.

When the transparent plastic material of the present invention is usedin farsighted eyeglass lenses, asthenopia can be prevented. Adjustmentability of human eyes is decreased with age, and becomes difficult tosee near objects and likely to feel fatigue. This phenomenon which isgenerally called farsightedness is said to be caused by a decrease inelasticity of the eye lens and a decrease in adjustment function withage. Farsighted eyeglass lenses are used to eliminate thus inconveniencedue to farsightedness. Single focus convex lenses have heretofore beenused as farsighted eyeglass lenses, but recently, double focus orprogressive multiple focus lenses are widely used to eliminatetroublesome change of glasses. By using such farsighted eyeglass lenses,the adjustment function of eyes tends to be made up and eye fatigue isreduced. However, there is eye fatigue of types which cannot beeliminated by farsighted eyeglass lenses designed mainly for improvingthe adjustment function of the eye. That is, myosis, shallowing ofanterior chamber, yellowing and hardening of an eye lens, or contractionof retina rear end may occur with age. Yellowing of eye lens increasesabsorption of short wavelength light, and hardening of eye lens scatterslight, increases the luminance on the retina surface, and reducescontrast vision. Myosis and an increase in optical density of the eyelens with age (yellowing of eye lens with age increases absorption ofshort wavelength region in visible light) increases an absolutethreshold of sight, which indicated as the product of quantity of lightwhich comes in eyes multipled by area of pupil. Such aging ofintraocular tissues causes myiodesopsia in a light place, a light veil,and dazzling of light, source or reflection. These effects appear as thephenomena the light of a car running in the opposite direction isdazzling, when direct reflection from the surface of an object or brightlight source comes in to sight, and when the white bright of a papercovers over letters while reading a book. The transparent plasticmaterial of the present invention can always be used in daily life, andcan block or reduce intense light of a wavelength region of high sightsensitivity and block ultraviolet light, and the above phenomena can beminimized to reduce or prevent eye fatigue.

Display filters, optical apparatus lenses and filters of cameras and thelike comprising the transparent plastic material of the presentinvention have properties to selectively block or reduce only light of aspecific wavelength.

(1) Since the transparent plastic material of the present inventioncontains the chemically stable complex compound of Formula (I) which hasgood compatibility with polymerizable monomers or thermoplastic resinsand selective absorptivity to light of a specific wavelength andultraviolet absorptivity, there is no variation in color, noprecipitation, high transparency, improved selective absorptivity tolight of a specific wavelength, and blocking of harmful ultravioletlight.

(2) Since the transparent plastic material of the present invention usesthe complex compound of Formula (I) which has good compatibility withhydrophobic polymerizable monomers, a water-soluble metal salt and ahydrophilic polymerizable monomer do not need to be used, and canimprove water resistance and dimensional stability.

(3) Since the transparent plastic material of the present inventioncontains the complex compound of Formula (I) which absorbs ultravioletlight, it is not necessary to add an ultraviolet absorber separately,and if such is to be added, since the amount of addition can besubstantially reduced, problems with compatibility such as precipitationof the ultraviolet absorber are eliminated, and deterioration of themechanical characteristics of the polymer is prevented.

(4) Optical articles comprising the transparent plastic material of thepresent invention can selectively block or reduce only light of awavelength which is dazzling to the human eye, and can block harmfulultraviolet light.

(5) Eyeglass lenses comprising the transparent plastic material of thepresent invention has properties to selectively block or reduce onlylight of a wavelength which is dazzling to the human eye, and can blockharmful ultraviolet light.

(6) Since eyeglass lenses comprising the transparent plastic material ofthe present invention has a glare-proof function to block or reducestrong light of a wavelength range of high sight sensitivity and canblock harmful ultraviolet light, these lenses protect the eyes fromultraviolet light and can reduce prevent eye fatigue.

(7) Farsighted eyeglass lenses, contact lenses, and display filterscomprising the transparent plastic material of the present inventionhave similar effects as shown in (5) and (6).

(8) Optical apparatus lenses and filters comprising the transparentplastic material of the present invention have a high transparency, animproved selective absorption function to light of a specificwavelength, and can block harmful ultraviolet light.

(9) Since the complex compound of Formula (I) used in the presentinvention has good compatibility with polymerizable monomers and ischemically stable, transparent plastic material and optical articles ofthe present invention can be obtained which have high transparency andhigh optical uniformity with no precipitation generated nor variation incolor in cast molding occurring.

(10) Since the complex compound of Formula (I) used in the presentinvention has good compatibility with thermoplastic resins and ischemically stable, and can be mixed and uniformly melted with moltenthermoplastic resins, the transparent plastic material and opticalarticles of the present invention can be obtained which have hightransparency and high optical uniformity with no precipitation generatednor variation in color in injection molding.

(11) The production method in which a composition comprising one or morepolymerizable monomers, a polymerization initiator or catalyst, and thecomplex compound of Formula (I) used in the present invention ispolymerized to form a thin film layer on a substrate comprising thetransparent plastic material of the present invention can be applied toall types of transparent plastic materials, since it can provide thetransparent plastic material and optical articles of the presentinvention by treatment after molding which have no differences in colordensity due to differences in thickness.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing the spectral characteristics of the lens ofExample 1:

FIG. 2 is a diagram showing the spectral characteristics of the lens ofExample 2;

FIG. 3 is a diagram showing the spectral characteristics of the lens ofExample 3;

FIG. 4 is a diagram showing the spectral characteristics of the lens ofExample 4;

FIG. 5 is a diagram showing the spectral characteristics of the moldingof Test Example 4;

FIG. 6 is a diagram showing the amount ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium of Test Example 4 vs.absorbance at the characteristic absorption wavelength of the neodymiumatom;

FIG. 7 is a diagram showing the thickness of the molding vs. absorbanceat 580 nm in the molding of Example 18;

FIG. 8 is a diagram showing the relationship between the content ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium and the degree offatigue in the molding of Example 24;

FIG. 9 is a diagram showing the relationship between the thickness ofthe molding after aquahydroxy(1-phenyl-1,3-butanedionato)neodymium andthe degree of fatigue in the molding of Example 24;

FIG. 10 is a diagram showing changes with the passage of time ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium in the molding of TestExample 5 under irradiation with a fluorescent lamp;

FIG. 11 is a diagram showing changes with the passage of time ofaquahydroxy(1-phenyl-1,3-butanedionato)erbium in the molding of TestExample 6 under irradiation with a fluorescent lamp;

FIG. 12 is a diagram showing changes with the passage of time ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium--styrene solution ofTest Example 8 under irradiation with a fluorescent lamp;

FIG. 13 is a diagram showing changes with the passage of time ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium(98%)/trisbenzoylacetonatoneodymium (2%)--styrene solution of TestExample 8 under irradiation with a fluorescent lamp;

FIG. 14 is a diagram showing changes with the passage of time oftrisbenzoylacetonatoneodymium of Test Example 8 under irradiation with afluorescent lamp;

FIG. 15 is a diagram showing an infrared absorption spectrum ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium complex;

FIG. 16 is a diagram showing a visible/ultraviolet absorption spectrumof a 2% toluene solution ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium complex;

FIG. 17 is a diagram showing an infrared absorption spectrum oftrisbenzoylacetonatoneodymium complex;

FIG. 18 is a diagram showing a visible/ultraviolet absorption spectrumof a 2% toluene solution of trisbenzoylacetontoneodymium complex;

FIG. 19 is a schematic view showing a steric structure ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium complex.

BEST MODE FOR PRACTICING THE INVENTION

The present invention will now be described in ever detail withreference to the examples. However, the present invention is not limitedto the examples.

Synthesis Examples of Two-Coordination Complex Compound

(SYNTHESIS EXAMPLE 1)

Synthesis of Aquahydroxy(1-phenyl-1,3-butanedionato)neodymium

To a solution of 32.4 g (0.20 mole) of benzoylacetone and 43.8 g (0.10mole) of neodymium nitrate dissolved in 120 ml of methanol, 120 ml of 4%aqueous ammonia solution was added dropwise. After the addition, themixture was reacted at 20° to 25° C. for 1 hour, the precipitatedblue-violet crystal was filtered, and washed with water to obtain acompound, which was subjected to elementary analysis (Nd content), watercontent analysis, and measurement of infrared absorption spectrum toobtain the following results.

Elementary Analysis: C20H21O6Nd=501.63

    ______________________________________                                                 Measured value                                                                         Calculated value                                            ______________________________________                                        C          47.94      47.88                                                   H          3.90       4.22                                                    ______________________________________                                    

Nd Content: measured 30.0% (calculated 28.8%)

Water Content: measured 4.1% (calculated 3.6%)

IR Spectrum (KBr, cm⁻¹): 3355, 3063, 1597, 1529, 1485, 1382, 1237, 714

From the above results, the resulting substance was confirmed to be (C₆H₅ COCHCOCH₃)₂ Nd(OH)(H₂ O). (Formula (1-1-a)).

(SYNTHESIS EXAMPLE 2)

Synthesis of Aquahydroxy(1-phenyl-1,3-butanedionato)erbium

To a solution of 32.4 g (0.20 mole) of benzoylacetone and 46.1 g (0.10mole) of erbium nitrate dissolved in 125 ml of methanol, 120 ml of 4%aqueous ammonia solution was added dropwise. After the addition, themixture was reacted at 20° to 25° C. for 1 hour, precipitatedrose-colored crystal was filtered, and washed with water to obtain acompound, which was subjected to elementary analysis (Er content), watercontent analysis, and measurement of infrared absorption spectrum toobtain the following results.

Elementary Analysis: C₂₀ H₂₁ O₆ Er=524.65

    ______________________________________                                                 Measured value                                                                         Calculated value                                            ______________________________________                                        C          45.79      45.78                                                   H          3.87       4.03                                                    ______________________________________                                    

Er Content: measured 32.5% (calculated 31.9%)

Water Content: measured 4.4% (calculated 3.4%)

IR Spectrum (KBr, cm⁻¹): 3620, 1600, 1525, 1486, 1394, 1283, 711

From the above results, the resulting substance was confirmed to be (C₆H₅ COCHCOCH₃)₂ Er(OH)(H₂ O) (Formula (1-1-b)).

(SYNTHESIS EXAMPLE 3)

Synthesis of aquahydroxy(phenacylphenylketonato)neodymium,aquahydroxy(1-phenyl-2-methyl-1,3-butanedionato)neodymium, andaquahydroxy(1-thiophenyl-1,3-butanedionato)neodymium

Synthesis was conducted using the same procedure as in Synthesis Example1 and Synthesis Example 2 except that benzoylacetone was replaced withphenacylphenylketone, or 1-phenyl-2-methyl-1,3-butanedione, or1-thiophenyl-1,3-butanedione.

The resulting substances were confirmed to be

Aquahydroxy(phenacylphenylketonato)neodymium of Formula (1-2-a),

Aquahydroxy(1-phenyl-2-methyl-1,3-butanedionato)neodymium of Formula(1-3-a), and

Aquahydroxy(1-thiophenyl-1,3-butanedionato)neodymium of Formula (1-4-a),respectively.

TEST EXAMPLES

Test Examples showing the effects of the present invention are describedbelow.

(Test Example 1)

Solubility test in polymerizable monomers

Aquahydroxy(1-phenyl-1,3-butanedionato)neodymium of Synthesis Example 1,aquahydroxy(1-phenyl-1,3-butanedionato)erbium of Synthesis Example 2,aquahydroxy(phenacylphenylketonato)neodymium.aquahydroxy(1-phenyl-2-methyl-1,3-butanedioriato)neodymium, andaquahydroxy(1-thiophenyl-1,3-butanedionato)neodymium of SynthesisExample 3 were soluble in styrene, divinylbenzene, phenyl methacrylate,tetrahydrofurfuryl methacrylate, methyl methacrylate, benzylmethacrylate, diallylphthalate, diethyleneglycolbisallylcarbonate, ando-chlorostyrene.

The three-coordination complex was also soluble in the monomer of theabove examples.

(Test Example 2)

Improvement of solubility of two-coordination complex in polymerizablemonomers

Results of dissolving the two-coordination complexaquahydroxy(1-phenyl-1,3-butanedionato)neodymium in individual monomersat 20° C. are shown in Table 4.

For comparison, the solubility of the three-coordination complextrisbenzoylacetonatoneodymium of Japanese Patent Application 05-502109(PCT/JP92/00883: International Laid-open WO93/01233; U.S. Ser. No.08/027,173) is shown in Table 4.

The above trisbenzoylacetonatoneodymium was synthesized by the methoddisclosed in Japanese Patent Application 05-502109 (PCT/JP92/00883;International Laid-open WO93/01233; U.S. Ser. No. 08/027,173).

                  TABLE 4                                                         ______________________________________                                                                      Dissolved                                       Monomer (g)      Complex Compound                                                                           Amount (g)                                      ______________________________________                                        Test Example 2                                                                Styrene     10.0     Aquahydroxy  30.0                                                             (1-phenyl-1,3-                                                                butanedionato)                                                                neodymium                                                Methyl      10.0     Aquahydroxy  25.0                                        methacrylate         (1-phenyl-1,3-                                                                butanedionato)                                                                neodymium                                                Benzyl      10.0     Aquahydroxy  30.0                                        methacrylate         (1-phenyl-1,3-                                                                butanedionato)                                                                neodymium                                                Comparative Example                                                           Styrene     10.0     Trisbenzoyl  2.5                                                              acetonato                                                                     neodymium                                                Methyl      10.0     Trisbenzoyl  2.0                                         methacrylate         acetonato                                                                     neodymium                                                Benzyl      10.0     Trisbenzoyl  2.5                                         methacrylate         acetonato                                                                     neodymium                                                ______________________________________                                    

As shown in the Table, it was confirmed that the two-coordinationcomplex is very high (about 15 times higher) in solubility compared withthe three-coordination complex.

From the above results, the following advantages can be asserted.

(1) Content of the two-coordination complex can be increased to a greatextent.

(2) Content of the two-coordination complex can be flexibly determinedaccording the application and purpose of the molding (lens).

As an example, sufficient effects (glare-proof function, eye fatigueprevention, etc.) can be obtained by increasing the content of thetwo-coordination complex when the thickness of the molding is to bereduced (central thickness of the lens is to be reduced). This is shownlater (shown in test examples).

(Test Example 3)

Results of dissolving the aquahydroxy(1-phenyl-1,3-butanedionato)erbiumsynthesized in Synthesis Example 2 in individual monomers at 20° C. areshown in Table 5. For comparison, the solubility oftrisbenzoylacetonatoerbium of Japanese Patent Application 05-502109(PCT/JP92/00883; International Laid-open WO93/01233: U.S. Ser. No.08/027,173) is shown in Table 5.

Trisbenzoylacetonatoerbium was synthesized by the method of "ProductionExample 2" disclosed in Japanese Patent Application 05-502109(PCT/JP92/00883; International Laid-open WO93/01233; U.S. Ser. No.08/027,173).

                  TABLE 5                                                         ______________________________________                                                                      Dissolved                                       Monomer (g)      Complex Compound                                                                           Amount (g)                                      ______________________________________                                        Test Example 3                                                                Styrene     10.0     Aquahydroxy  30.0                                                             (1-phenyl-1,3-                                                                butanedionato)                                                                erbium                                                   Methyl      10.0     Aquahydroxy  25.0                                        methacrylate         (1-phenyl-1,3-                                                                butanedionato)                                                                erbium                                                   Benzyl      10.0     Aquahydroxy  30.0                                        methacrylate         (1-phenyl-1,3-                                                                butanedionato)                                                                erbium                                                   Comparative Example                                                           Styrene     10.0     Trisbenzoyl  2.5                                                              acetonato                                                                     erbium                                                   Methyl      10.0     Trisbenzoyl  2.0                                         methacrylate         acetonato                                                                     erbium                                                   Benzyl      10.0     Trisbenzoyl  2.5                                         methacrylate         acetonato                                                                     erbium                                                   ______________________________________                                    

(Test Example 4)

Changes in content of the two-coordination complex

To 36 parts by weight of styrene, 60 parts by weight of2,2-bis(4-methacroyloxyethoxy-3,5-dibromophenyl)propane, and 4 parts byweight of diethyleneglycolbisallylcarbonate, 1 phm ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium of synthesis example 2was mixed,and then 1 phm of t-butylperoxyneodecanoate as an initiator isadded and filtered. The filtrate was injected into a mold, comprisingtwo glass flat plates and a gasket of ethylene-vinyl acetatecopolymer,whose the clearance is 2 mm.

Then, the filtrate was heated at 30° C. for 4 hours, linearly increasedfrom 30° C. to 50° C. over a period of 10 hours, linearly increased from50° C. to 80° C. in 2 hours, maintained at 80° C. for 1 hour, and cooledto 70° C. in 2 hours.

The gasket was removed, and the resulting molding was separated from theglass flat plates. The resulting molding was annealed at 100° C. for 2hours.

In the same method, flat moldings were obtained with the amounts ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium of 2 phm, 5 phm, and 10phm.

The thus obtained moldings had high transparency.

The spectral characteristics of the moldings are shown in FIG. 5. Asshown in FIG. 5, the transmittance was 68% at 580 nm, which is thecharacteristic absorption wavelength of neodymium atom, when the contentof aquahydroxy(1-phenyl-1,3-butanedionato)neodymium was 1 phm,18% whenthe content was 5 phm, and 2% when the content was 10 phm.

The relationship between the content ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium and the absorbance at580 nm of the resulting molding is shown in FIG. 6.

As shown in FIG. 6, the glare-proof effect was comfirmed to increaseswith increasing content ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium of the resultingtransparent molding.

These results show that since the solubility of the three-coordinationcomplex, the range of content for forming a transparent molding isconsiderably increased, and the amount of the two-coordination complexcan be flexibly selected according to the purpose and application.

(Test Example 5)

Differences in changes over time and coloring

Four grams of aquahydroxy(1-phenyl-1,3-butanedionato)neodymium wasdissolved in 100 g of styrene, and checked for changes with the passageof time under irradiation with a fluorescent lamp (700 lx) and in a darkplace at 20° C. The results are shown in FIG. 10. Under any of theconditions under irradiation with the fluorescent lamp and the darkplace, the styrene solution which was initially in blue-violet showed nochange after 2 weeks, and was blue-violet in color.

As a comparison with the present example, 4 g oftrisbenzoylacetonatoneodymium was dissolved in 100 g of styrene, andchecked for changes with the passage of time under irradiation with afluorescent lamp (700 lx) and in a dark place at 20° C. The results areshown in FIG. 10. The solution which was initially blue-violet becamegreen with the passage of time, and after the passage of 2 weeks, thesolution was yellow-brown and a yellow-brown precipitation wasgenerated. Further, in the dark, change, were smaller as compared withthose under irradiation with the fluorescent lamp, but the color changedto yellow-green after 2 weeks.

(Test Example 6)

Four grams of aquahydroxy(1-phenyl-1,3-butanedionato)erbium wasdissolved in 100 g of styrene, and checked for changes with the passageof time under irradiation with a fluorescent lamp (700 lx) and in thedark at 20° C. The results are shown in FIG. 11. Under any of theconditions under irradiation with the fluorescent lamp and in the dark,the styrene solution which was initially rose showed no change after 2weeks, and was rose-colored.

As a comparison with the present example, 4 g oftrisbenzoylacetonatoerbium was dissolved in 100 g of styrene, andchecked for changes with the passage of time under irradiation with afluorescent lamp (700 lx) and in the dark at 20° C. The results areshown in FIG. 11. The solution which was initially rose-colored becamebrown with the passage of time, and after the passage of 2 weeks, thesolution was yellow-brown and a yellow-brown precipitate was generated.Further, in the dark, changes were smaller as compared with those underirradiation with the fluorescent lamp, but the color changed to brownafter 2 weeks.

(Test Example 7)

Ten grams of aquahydroxy(1-phenyl-1,3-butanedionato)neodymium wasdissolved in 100 g of methyl butanedionato)neodymium was dissolved in100 g of methyl methacrylate, and checked for changes with the passageof time under irradiation with a fluorescent lamp (700 lx) and in thedark at 20° C. As a comparison, 10 g of trisbenzoylacetonatoneodymiumwas dissolved in 100 g of methyl methacrylate, and checked for changeswith the passage of time under the same conditions. The results areshown in Table 6.

                  TABLE 6                                                         ______________________________________                                                              Time                                                                         Test              After 2                                Complex Compound                                                                          Monomer  Condition  Initial                                                                              Weeks                                  ______________________________________                                        Test Example                                                                  Aquahydroxy Methyl   Under      Blue-  Blue-                                  (1-phenyl-1,3-                                                                            methacry-                                                                              fluorescent                                                                              violet violet                                 butanedionato)                                                                            late     lamp (700 lx)                                                                            No pre-                                                                              No pre-                                neodymium            at 20° C.                                                                         cipita-                                                                              cipita-                                                                tion   tion                                                        Dark place Blue-  Blue-                                                       at 20° C.                                                                         violet,                                                                              violet,                                                                No pre-                                                                              No pre-                                                                cipita-                                                                              cipita-                                                                tion   tion                                   Comparative Example                                                           Trisbenzoyl Methyl   Under      Blue-  Yellow-                                acetonato   methacry-                                                                              fluorescent                                                                              violet brown                                  neodymium   late     lamp (700 lx)                                                                            No pre-                                                                              Precipi-                                                    at 20° C.                                                                         cipita-                                                                              tation                                                                 tion   occurs                                                      Dark place Blue-  Yellow-                                                     at 20° C.                                                                         violet,                                                                              green                                                                  No pre-                                                                              No pre-                                                                cipita-                                                                              cipita-                                                                tion   tion                                   ______________________________________                                    

(Test Example 8)

Changes over time of A combination of A two-coordination complex and Athree-coordination complex

(1) Two grains of aquahydroxy(1-phenyl-1,3-butanedionato)neodymium ofsynthesis example I was dissolved in 100 g of styrene, and checked forchanges with the passage of time (0, 7, 15, and 23 days) by absorbanceunder irradiation with a fluorescent lamp (700 lx) at 20° C. (FIG. 12).

(2) In the same method, 2 g ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium containing 2% oftrisbenzoylacetontoneodium as an impurity was dissolved in 100 g ofstyrene, and checked for changes with the passage of time (0, 7, 15, and23 days) (FIG. 13).

(Note: this sample was obtained in the initial stage of study onsynthesis of the two-coordination complex.)

(3) Trisbenzoylacetonatoneodymium was also checked for changes with thepassage of time (0, 3, 7, and 15 days) (FIG. 14).

The individual test results are shown in the Figures.

According to the result of (1) shown in FIG. 12, no changes were notedwith the passage of time.

According to the result of (2) shown in FIG. 13, slight changes werenoted with the passage of time. However, the rate of change over time isslower as compared with (3) of the three-coordination complex alone.

According to the result of (3) shown in FIG. 14, considerable changesover time were noted.

DETAILED DESCRIPTION OF PREFERRED EXAMPLES

Preferred examples of the present invention are described below, but thepresent invention is not limited to these examples.

(EXAMPLE 1)

Photopolymerizable composition comprising:

    ______________________________________                                        Bifunctional urethane methacrylate of                                                                   50 parts                                            Formula (11)              by weight                                           Polyethyleneglycol dimethacrylate of                                                                    10 parts                                            Formula (12)              by weight                                           Phenyl methacrylate       40 parts                                                                      by weight                                           2-Hydroxy-2-methyl-1-phenylpropan-1-one                                                                 1 phm                                               (Merck Dalocure-1173)                                                         t-Butylperoxyisopropylcarbonate                                                                         0.5 phm                                             ______________________________________                                    

was mixed with 3 parts by weight ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium of synthesis example 1,and dissolved at 50° C. ##STR15##

The resulting mixture was blue-violet colored and transparent. Themixture was injected into a mold comprising a mirror-finishied glassmold with an outer diameter of 80 mm and a curvature radius of 386 mm, aglass mold with an outer diameter of 80 mm and a curvature radius of 65mm, and a gasket formed of ethylene-vinyl acetate copolymer to form aconcave lens with a central thickness of 1.5 mm. The mold wascontinuously irradiated for 3 minutes with a 2 kW high-pressure mercurylamp from both sides of the mold at an illuminance of 400 mW/cm² toharden the mixture. When the mold temperature was decreased to 60° C.,the lens was released from the glass mold. After the lens was washed, itwas annealed at 100° C. for 2 hours.

The resulting lens was blue-green colored, the light transmissivity at580 nm was as low as 30%, blocked ultraviolet light of less than 400 nmin wavelength, and the transmissivity of other wavelength area was morethan 90%. The spectral characteristics of the lens of the presentexample are shown in FIG. 1.

The lens was surface treated with a commercial ultraviolet curing typeorganic hard coating.

As a comparative example, a lens free ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium was prepared, dyed tothe same color as the above lens, and surface treated same as theexample. The example lens and the comparative example lens were worn forevaluation of the glare. As a result, glare of direct sunlight, andglare of the head light of a car running in the opposite direction atnight were greatlly reduced as compared with the comparative examplelens.

The lens of the present example provided thereon with a reflection-prooffilm was even smaller in flickering of light. Further, after the lenswas allowed to stand in a high temperature and high humidity environmentat 60° C. and 90% RH for one week, the absorptivity was 1.0% and nocracking was noted in the deposited film.

(EXAMPLE 2)

Two parts by weight of aquahydroxy(1-phenyl-1,3-butanedionato)neodymium,36 parts by weight of styrene, 60 parts by weight of2,2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane, 4 parts byweight of diethyleneglycolbisallylcarbonate, and I part by weight oft-butylperoxyneodecanoate were mixed and filtered. The filtrate wasinjected into a mold comprising two glass molds and a gasket ofethylene-vinyl acetate copolymer to obtain lenses of 2 mm of centerthickness. Then, the filtrate was heated at 30° C. for 4 hours, linearlyincreased from 30° C. to 50° C. over a period of 10 hours, linearlyincreased from 50° C. to 80° C. in 2 hours, maintained at 80° C. for 1hour, cooled from 80° C. to 70° C. in 2 hours, and the lens was releasedfrom the mold. Further, the resulting lens was annealed at 100° C. for 2hours.

The resulting lens had a refractive index of 1.59, the lighttransmissivity was as low as 40% at 580 nm, blocked ultraviolet light ofless than 400 nm in wavelength, and the transinissivity of otherwavelength areas was more than 85%. Therefore, the lens was one whichhad properties to selectively block or reduce only light of a specificwavelength but did not reduce other visible light, had a superiorglare-proof function in light adaptation sight, and blocked ultravioletlight. Further, after the lens was allowed to stand in a hightemperature and high humidity environment at 60° C. and 90% RH for oneweek, the water absorption was 1.0%. This value was much better thanComparative Example 5 which is a system using neodymium acetate as awater-soluble neodymium salt. After the lens was provided on the surfacewith an inorganic deposition film as a reflection-proof film and allowedto stand in the above high temperature and high humidity environment forone week, no cracking was noted in the deposition film.

FIG. 2 shows the spectral characteristics of the lens of the presentexample.

The lens of the present example was attached to an eyeglass frame andsubjected to a wearing test. The test will be described below.

The lens used was provided with a reflection-proof film, and a lens ofthe same composition as the example lens except thataquahydroxy(1-phenyl-1,3-butanedionato)neodymium was removed and dyed tothe same color as the example lens was used as a comparative sample. Thetest was conducted for randomly selected 50 men and women (Age ofexaminees; 20s:20%, 30s:30%, 40s:30%, 50s:20%). Answers were evaluatedin a three-point method: Yes (feel so): 2 points, (feel something likethat): 1 point, No (no change): 0 point. The test results are shownbelow.

                                      TABLE 7                                     __________________________________________________________________________                                Answer                                                                        Example                                                                            Compara-                                     Question                    2    tive                                         __________________________________________________________________________      No glare outdoor, in fine.                                                                              1.8  0                                              No glare while driving a car.                                                                           1.8  0                                              No glare in outdoor sporting.                                                                           1.8  0                                              No glare of headlight of car in opposite direction at                                                   1.7ht.                                                                             0                                              No glare of paper surface while reading.                                                                1.3  0                                              No glare while watching television.                                                                     1.8  0                                              No glare of display in working on a wordprocessor.                                                      1.9  0                                              Clear view of an object outdoor, in fine.                                                               1.8  0                                              Clear view of around while driving a car.                                                               1.8  0                                            10.                                                                             Letters on paper are read clearly while reading.                                                        1.6  0                                              Clear view of television screen.                                                                        1.8  0                                              Clear view of display screen while working on a word                                                    1.8  0                                              processor.                                                                    Clear view of object in a light place from a dark place.                                                1.8  0                                              No eye fatigue when using outdoor, in fine.                                                             1.9  0                                              No eye fatigue when driving a car.                                                                      1.7  0                                              No eye fatigue when driving a car at night.                                                             1.7  0                                              No eye fatigue in reading or writing.                                                                   1.7  0                                              No eye fatigue when watching television for a long time.                                                1.8  0                                              No eye fatigue when looking at a movie.                                                                 1.0  0                                            20.                                                                             No eye fatigue when looking at a display while working on                                               1.8  0                                              wordprocessor for a long time.                                              __________________________________________________________________________

80% of the examinees observed a glare reduction, effect 70% observed aneye fatigue reduction effect.

(EXAMPLE 3)

Four parts by weight of aquahydroxy(1-phenyl-1,3-butanedionato)erbium,36 parts by weight of styrene, 60 parts by weight of2,2-bis(4-methacroyloxyethoxy-3,5-dibromophenyl)propane, 4 parts byweight of diethyleneglycolbisallylcarbonate, and 1 part by weight oft-butylperoxyneodecanoate were mixed and filtered. The filtrate wasinjected into a mold comprising two glass molds and a gasket ofethylene-vinyl acetate copolymer to obtain lenses of 2 mm of centerthickness. Then, the filtrate was heated at 30° C. for 4 hours, linearlyincreased from 30° C. to 50° C. over a period of 10 hours, linearlyincreased from 50° C. to 80° C. in 2 hours, maintained at 80° C. for 1hour, cooled from 80° C. to 70° C. in 2 hours, and the lens was releasedfrom the mold. Further, the resulting lens was annealed at 100° C. for 2hours.

The resulting lens had a refractive index of 1.59, the lighttransmissivity was as low as 40% at 520 nm, blocked ultraviolet light ofless than 400 nm in wavelength, and the transinissivity of otherwavelength areas was more than 85%. Therefore, the lens was one whichhad properties of selectively blocking or reducing light only of aspecific wavelength but did not reduce other visible light, had asuperior glare-proof function on dark adaptation sight, and blockedultraviolet light. Further, after the lens was allowed to stand in ahigh temperature and high humidity environment at 60° C. and 90% RH forone week, the water absorption was 1.0%. This value was much better thanComparative Example 6 which is a system using erbium acetate as awater-soluble erbium salt. After the lens was provided on the surfacewith an inorganic deposition film as a reflection-proof film and allowedto stand in the above high temperature and high humidity environment forone week, no cracking was noted in the deposition film.

The spectral characteristics of the present example are shown in FIG. 3.

(EXAMPLE 4)

Five parts by weight of aquahydroxy(1-phenyl-1,3-butanedionato)neodymiumand 5 parts by weight of aquahydroxy(1-phenyl-1,3-butanedionato)erbium,36 parts by weight of styrene, 60 parts by weight of2,2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane, 4 parts byweight of diethyleneglycolbisallylcarbonate, and 1 part by weight oft-butylperoxyneodecanoate were mixed and filtered. The filtrate wasinjected into a mold comprising two glass molds and a gasket ofethylene-vinyl acetate copolymer to obtain lenses of 1.5 mm of centerthickness. Then, the filtrate was heated at 30° C. for 4 hours, linearlyincreased from 30° C. to 50° C. over a period of 10 hours, linearlyincreased from 50° C. to 80° C. in 2 hours, maintained at 80° C. for 1hour, cooled from 80° C. to 70° C. in 2 hours, and the lens was releasedfrom the mold. Further, the resulting lens was annealed at 100° C. for 2hours.

The resulting lens had a refractive index of 1.59, the lighttransmissivity was as low as 30% at 520 nm and 30% at 580 nm, andblocked ultraviolet light of less than 400 nm in wavelength, and thetransmissivity of other wavelength area was more than 85%. Therefore,the lens was one which had properties to selectively block or reduceonly light of a specific wavelength but did not reduce other visiblelight, had a superior glare-proof function in light adaptation sight,and blocked ultraviolet light. Further, after the lens was allowed tostand in a high temperature and high humidity environment at 60° C. and90% RH for one week, the water absorption was 1.0%. After the lens wasprovided on the surface with an inorganic deposited film as areflection-proof film and allowed to stand in the above high temperatureand high humidity environment for one week, no cracking was noted in thedeposited film.

The spectral characteristics of the present example are shown in FIG. 4.

The lens of the present example was attached to a frame and subjected toa wearing test. This test is be described below.

The lens used was provided with a reflection-proof film, and a lens ofthe same composition as the example lens except thataquahydroxy(1-phenyl-1,3-butanedionato)neodymium andaquahydroxy(1-phenyl-1,3-butanedionato)erbium were removed and dyed tothe same color as the example lens was used as a comparative sample. Thetest was conducted for randomly selected 50 men and women (Age ofexaminees; 20s:20%, 30s:30%, 40s:30%, 50s:20%). Answers were evaluatedin a three-point method: Yes (feel so): 2 points, (feel something likethat): 1 point, No (no change): 0 point. The test results are shown intable 8 below.

                                      TABLE 8                                     __________________________________________________________________________                                Answer                                                                        Example                                                                            Compara-                                     Question                    2    tive                                         __________________________________________________________________________      No glare outdoor, in fine.                                                                              1.9  0                                              No glare during driving a car.                                                                          1.9  0                                              No glare in outdoor sporting.                                                                           1.9  0                                              No glare of headlight of car in opposite direction at                                                   1.9ht.                                                                             0                                              No glare of paper surface while reading.                                                                1.7  0                                              No glare while watching television.                                                                     1.9  0                                              No glare of display in working on a wordprocessor.                                                      1.9  0                                              Clear view of an object outdoor, in fine.                                                               1.9  0                                              Clear view of around while driving a car.                                                               1.9  0                                            10.                                                                             Letters on paper are read clearly while reading.                                                        1.7  0                                              Clear view of television screen.                                                                        1.9  0                                              Clear view of display screen while working on a word                                                    1.9  0                                              processor.                                                                    Clear view of object in a light place from a dark place.                                                1.8  0                                              No eye fatigue when using outdoor, in fine.                                                             1.9  0                                              No eye fatigue when driving a car.                                                                      1.9  0                                              No eye fatigue when driving a car at night.                                                             1.9  0                                              No eye fatigue in reading or writing.                                                                   1.9  0                                              No eye fatigue when watching television for a long time.                                                1.9  0                                              No eye fatigue when looking at a movie.                                                                 1.4  0                                            20.                                                                             No eye fatigue when looking at a display while working on                                               1.9  0                                              wordprocessor for a long time.                                              __________________________________________________________________________

(EXAMPLE 5)

Using the same procedure as in Example 2, 4 parts by weight ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium, 36 parts by weight ofstyrene, 60 parts by weight of2,2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane, 4 parts byweight of diethyleneglycolbisallylcarbonate, and 1 part by weight oft-butylperoxyneodecanoate were mixed and filtered. The filtrate wasinjected into a mold comprising two progressive multiple focus lensglass molds (Seiko Epson HIGHLOAD MXP-1 MILD) and a gasket ofethylene-vinyl acetate copolymer. Then, the filtrate was heated at 30°C. for 4 hours, linearly increased from 30° C. to 50° C. over a periodof 10 hours, linearly increased from 50° C. to 80° C. in 2 hours,maintained at 80° C. for 1 hour, cooled from 80° C. to 70° C. in 2hours, and the lens was released from the mold. Further, the resultinglens was annealed at 100° C. for 2 hours.

The lens of the present example was attached to an eyeglass frame andsubjected to a wearing test. The test is be described below.

The lens used was provided with a reflection-proof film, and a lens ofthe same composition as the example lens except thataquahydroxy(1-phenyl-1,3-butanedionato)neodymium was removed and dyed tothe same color as the example lens was used as a comparative sample. Thetest was conducted for randomly extracted 100 men and women at 40 to 60ages level. To a plurality of questions on glare reduction, eye fatiguereduction, contrast, and the like, the answers were evaluated in afive-point method: Very Good: 5 points, Good: 4 points, Normal: 2points, Poor: 1 point, Very Poor: 1 point. The points were averaged foreach item. The results are shown below.

                  TABLE 9                                                         ______________________________________                                                   Example 5       Comparative                                        Item         Average Variance  Average                                                                             Variance                                 ______________________________________                                        Glare reduction                                                                            4.50    0.4       2.90  0.2                                      Eye fatigue prevention                                                                     4.80    0.3       2.88  0.1                                      Lightness of sight                                                                         4.40    0.2       4.33  0.3                                      Contrast     4.60    0.3       2.80  0.2                                      ______________________________________                                    

(EXAMPLE 6)

Four parts by weight of aquahydroxy(phenacylphenylketonato)neodymium, 36parts by weight of styrene, 60 parts by weight of2,2-bis(4-methacroyloxyethoxy-3,5-dibromophenyl)propane, 4 parts byweight of diethyleneglycolbisallylcarbonate, and 1 part by weight oft-butylperoxyneodecanoate were mixed and filtered. The filtrate wasinjected into a mold comprising two glass molds and a gasket ofethylene-vinyl acetate copolymer. Then, the filtrate was heated at 30°C. for 4 hours, linearly increased from 30° C. to 50° C. over a periodof 10 hours, linearly increased from 50° C. to 80° C. in 2 hours,maintained at 80° C. for 1 hour, cooled from 80° C. to 70° C. in 2hours, and the lens was released from the mold. Further, the resultinglens was annealed at 100° C. for 2 hours.

The resulting lens had a refractive index of 1.59, the lighttransinissivity was as low as 40% at 580 nm, and blocked ultravioletlight of less than 400 nm in wavelength, and the transinissivity ofother wavelength areas was more than 85%. Therefore, the lens was onewhich had properties to selectively block or reduce only light of aspecific wavelength but did not reduce other visible light, had asuperior glare-proof function in light adaptation sight, and blockedultraviolet light. Further, after the lens was allowed to stand in ahigh temperature and high humidity environment at 60° C. and 90% RH forone week, the water absorption was 1.0%. This value was much better thanComparative Example 5 which is a system using neodymium acetate as awater-soluble neodymium salt. After the lens was provided on the surfacewith an inorganic deposition film as a reflection-proof film and allowedto stand in the above high temperature and high humidity environment forone week, no cracking was noted in the deposition film.

(EXAMPLE 7)

Four parts by weight ofaquahydroxy(1-phenyl-2-methyl-1,3-butanedionato)neodymium, 36 parts byweight of styrene, 60 parts by weight of2,2-bis(4-methacroyloxyethoxy-3,5-dibromophenyl)propane, 4 parts byweight of diethyleneglycolbisallylcarbonate, and 1 part by weight oft-butylperoxyneodecanoate were mixed and filtered. The filtrate wasinjected into a mold comprising two glass molds and a gasket ofethylene-vinyl acetate copolymer. Then, the filtrate was heated at 30°C. for 4 hours, linearly increased from 30° C. to 50° C. over a periodof 10 hours, linearly increased from 50° C. to 80° C. in 2 hours,maintained at 80° C. for 1 hour, cooled from 80° C. to 70° C. in 2hours, and the lens was released from the mold. Further, the resultinglens was annealed at 100° C. for 2 hours.

The resulting lens had a refractive index of 1.59, the lighttransmissivity was as low as 40% at 580 nm, blocked ultraviolet light ofless than 400 nm in wavelength, and the transmissivity of otherwavelength areas was more than 85%. Therefore, the lens was one whichhad properties to selectively block or reduce only light of a specificwavelength but did not reduce other visible light, had a superiorglare-proof function in dark adaptation sight, and blocked ultravioletlight. Further, after the lens was allowed to stand in a hightemperature and high humidity environment at 60° C. and 90% RH for oneweek, the water absorption was 1.0%. This value was much better thanComparative Example 5 which is a system using neodymium acetate as awater-soluble neodymium salt. After the lens were provided on thesurface with an inorganic deposited film as a reflection-proof film andallowed to stand in the above high temperature and high humidityenvironment for one week, no cracking was noted in the deposited film.

(EXAMPLE 8)

Four parts by weight ofaquahydroxy(1-thiophenyl-1,3-butanedionato)neodymium, 36 parts by weightof styrene, 60 parts by weight of2,2-bis(4-methacroyloxyethoxy-3,5-dibromophenyl)propane, 4 parts byweight of diethyleneglycolbisallylcarbonate, and 1 part by weight oft-butylperoxyneodecanoate were mixed and filtered. The filtrate wasinjected into a mold comprising two glass molds and a gasket ofethylene-vinyl acetate copolymer. Then, the filtrate was heated at 30°C. for 4 hours, linearly increased from 30° C. to 50° C. over a periodof 10 hours, linearly increased from 50° C. to 80° C. in 2 hours,maintained at 80° C. for 1 hour, cooled from 80° C. to 70° C. in 2hours, and the lens was released from the mold. Further, the resultinglens was annealed at 100° C. for 2 hours.

The resulting lens had a refractive index of 1.59, the lighttransmissivity was as low as 40% at 580 nm, blocked ultraviolet light ofless than 400 nm in wavelength, and transmissivity of other wavelengtharea was more than 85%. Therefore, the lens was one which had propertiesto selectively block or reduce only light of a specific wavelength butdid not reduce other visible light, had a superior glare-proof functionin dark adaptation sight, and blocked ultraviolet light. Further, afterthe lens was allowed to stand in a high temperature and high humidityenvironment at 60° C. and 90% RH for one week, the water absorption was1.0%. This value was much better than Comparative Example 6 which is asystem using neodymium acetate as a water-soluble neodymium salt. Afterthe lens was provided on the surface with an inorganic deposited film asa reflection-proof film and allowed to stand in the above hightemperature and high humidity environment for one week, no cracking wasnoted in the deposited film.

(EXAMPLE 9)

Four parts by weight of aquahydroxy(1-phenyl-1,3-butanedionato)neodymiumwas added to a reaction mixture comprising 52 parts by weight ofxylylenediisocynate, 48 parts by weight of4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 0.5 part by weight ofdibutyltindilaurate as a catalyst, and a small amount of alkyl acidphosphate ester as a release agent, and deaerated for 20 minutes whilemixing. The reaction mixture was injected into a mold comprising twoglass molds and a gasket of ethylene-vinyl acetate copolymer, graduallyincreased in temperature from 40° C. to 90° C. in a hot airrecirculation oven, and after being maintained at 90° C. for 1 hour,cooled to 60° C. in 1 hour. The lens, obtained by releasing from themold, was annealed at 100° C. for 2 hours to remove internal stress inthe lens. The resulting lens was a blue-green transparent one with arefractive index of 1.66. The light transmissivity of the lens was aslow as 40% at 580 nm, blocked ultraviolet light of less than 400 nm inwavelength, and transmissivity of other wavelength area was more than85%. Therefore, the lens was one which had properties to selectivelyblock or reduce only light of a specific wavelength but did not reduceother visible light, had a superior glare-proof function in lightadaptation sight, and blocked ultraviolet light. Further, after the lenswas allowed to stand in a high temperature and high humidity environmentat 60° C. and 90% RH for one week, the water absorption was 1.3%. Afterthe lens was provided on the surface with an inorganic deposition filmas a reflection-proof film and allowed to stand in the above hightemperature and high humidity environment for one week, no cracking wasnoted in the deposition film.

(EXAMPLE 10)

To a silicone-based hard coating solution comprising 28 parts by weightof hydrolysis product of 3-glycidoxypropyltrimethoxysilane, 27.5 partsby weight of colloidal silica (SiO2), 41.9 parts by weight ofglycerolpolyglycidylether, 2.1 parts by weight of magnesium perchlorate,0.5 part by weight of 4.4-thiobis-(3-methyl-6-t-butylphenol), 0.1 partby weight ofdimethylsiloxane-methyl(polyoxyethylene)-methyl(polyoxyethylene-methyl(polyoxypropylene)-siloxanecopolymer, and a solvent, 30 parts by weight ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium was added anddissolved. The solution was coated on a lens comprisingpolyethyleneglycolbisallylcarbonate, heated at 100° C. for 1 hour, andfurther heated at 130° C. for 2 hours. As a result, an eyeglass lens wasobtained which had a high surface hardness, a transmissivity of 60% at580 nm and a transmissivity of other wavelength areas of more than 85%,and a glare-proof function.

(EXAMPLE 11)

95 Parts by weight of methylmethacrylale, 4 parts by weight oftriethyleneglycoldimethacrylate, 2 parts by weight ofaquahydroxy(1-phenyl-1,3-butanedionato)neodyinium, and 0.2 part byweight of azobis(2,4-dimethylvaleronitrile) were thoroughly mixed, themixture was placed in a glass tube, the inside was repeatedly deaeratedwhile purging with nitrogen, and sealed under vacuum. The sealed tubewas heated at 30° C. for 10 hours, at 40° C. for 5 hours, at 60° C. for3 hours, at 70° C. for 3 hours, and further heated in a hot airrecirculation oven at 100° C. for 2 hours to obtain a round rod. Theresulting round rod was cut and ground to prepare a contact lens.

The contact lens had a transmissivity of as low as 70% at 580 nm, andblocked ultraviolet light of less than 400 nm, and the transmissivity ofother wavelength areas was more than 85%.

(EXAMPLE 12)

93 Parts by weight of 2-hydroxyethylmethacrylate, 2 parts by weight ofethyleneglycoldimethacrylate, 5 parts by weight ofaquahydroxy(1-phenyl-1,3-butanedionato)erbium, and 0.05 part by weightof azobis(2,4-dimethylvaleronitrile) as a polymerization initiator werethoroughly mixed. The mixture was placed in a glass tube, the inside wasrepeatedly deaerated while purging with nitrogen, and sealed undervacuum. The sealed tube was heated in hot water at 30° C. for 10 hours,at 40° C. for 5 hours, at 60° C. for 3 hours, at 70° C. for 3 hours, andfurther heated in a hot air recirculation oven at 100° C. for 2 hours toobtain a round rod. The resulting round rod was cut and ground toprepare a contact lens. The contact lens was swollen and washed in purewater, immersed in physiological saline to complete dissolution ofsoluble substances. Aquahydroxy(1-phenyl-1,3-butanedionato)erbium wasnot detected in the dissolved substances.

The contact lens had a transmissivity of as low as 55% at 520 nm, andblocked ultraviolet light of less than 400 nm, and the transmissivity ofother wavelength areas was more than 85%.

(EXAMPLE 13)

45 Parts by weight of 2,2,2-trifluoroethylmethacrylate, 40 parts byweight of tris(trimethylsiloxy)silylpropyl methacrylate, 10 parts byweight of 2-hydroxyethylmethacrylate, 3 parts by weight ofethyleneglycoldimethacrylate, 2 parts by weight ofaquahydroxy(1-phenyl-1,3-butanedionato)neodimium, 2 parts by weight ofaquahydroxy(1-phenyl-1,3-butanedionato)erbium, and 0.2 part by weight ofazobis(2,4-dimethylvaleronitrile) as a polymerization initiator werethoroughly mixed, the mixture was placed in a glass tube, the inside wasrepeatedly deaerated while purging with nitrogen, and sealed undervacuum. The sealed tube was heated in hot water at 30° C. for 10 hours,at 40° C. for 5 hours, at 60° C. for 3 hours, at 70° C. for 3 hours, andfurther heated in a hot air recirculation oven at 100° C. for 2 hours toobtain a round rod. The resulting round rod was cut and ground toprepare a contact lens. The contact lens had a transmissivity of as lowas 70% at 520 nm and 580 nm, and blocked ultraviolet light of less than400 nm, and the transinissivity of other wavelength area was more than85%.

In a dissolution test, dissolution ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium, andaquahydroxy(1-phenyl-1,3-butanedionato)erbium was not noted.

(EXAMPLE 14)

To a hard coating solution comprising:

    ______________________________________                                        Bifunctional urethane methacrylate of                                                                  20 parts                                             Formula (11)             by weight                                            Dipentaerythritol hexaacrylate                                                                         30                                                   Ethyleneoxide-modified succinic acid                                                                    5                                                   acrylate of the following Formula(22)                                         2-Hydroxypropylmethacrylate                                                                            20                                                   Isobornylacrylate        30                                                   2-Hydroxy-2-methyl-1-phenylpropane-1-one                                                                2                                                   ______________________________________                                    

10 parts by weight of aquahydroxy(1-phenyl-1,3-butanedionato)neodymiumwas added and mixed. The hard coating solution was coated on atransparent polymethylmethacrylate plate of 200 mm×200 mm×2 mm, with thesurface degreased, and irradiated with an 80 W/cm high-pressure mercurylamp for 30 seconds to obtain a hard coat film with a pencil hardness of8H. The composite had a transmissivity of as low as 60% at 580 nm,blocked ultraviolet light of less than 400 nm, and transmissivity ofother wavelength area was more than 85%. Therefore, the lens was onewhich had properties to selectively block or reduce only light of aspecific wavelength but did not reduce other visible light, had asuperior glare-proof function in light adaptation sight, and blockedultraviolet light. ##STR16##

(EXAMPLE 15)

In 100 parts by weight of methylmethacrylate, 5 parts by weight ofaquahydroxy(phenacylphenylketonato)neodymium and 5 parts by weight ofaquahydroxy(phenacylphenylketonato) erbium were dissolved, and 2 partsby weight of benzoylperoxide was further added as a polymerizationinitiator and mixed. The mixture was placed in a sealable pressurevessel, connected to a vacuum line, thoroughly purged with nitrogenwhile cooling in a dry ice-methanol bath, sealed under vacuum, and blockpolymerized at 85° C. The product was formed to a display filter usingan injection molding machine. The molding was gray-colored transparentarticle, and had an absorption at 520 nm and 580 nm. Thetransmissivities at both wavelengths were 20%, respectively. Further, itblocked ultraviolet light of less than 400 nm.

When the molding was used as a display filter, glare of the screen waseliminated, and contrast was improved without darkening the screen.Further, eye fatigue was not noted after looking the display for a longtime.

Similar effects could be obtained when optical apparatus lenses andfilters, and lighting apparatus covers were prepared using the sameprocedure.

(EXAMPLE 16)

To 100 parts by weight of polymethylmethacrylate, 5 parts by weight ofaquahydroxy(1-phenyl-1,3-butanedionato) neodymium and 5 parts by weightof aquahydroxy(1-phenyl-1,3-butanedionato)erbium were mixed in aninjection molding machine, and molded to a display filter. The moldingwas a gray-colored transparent article, and had an absorption at 520 nmand 580 nm.

Transmissivities at both wavelengths were 20%, respectively, and itblocked ultraviolet of less than 400 nm.

When the molding was used as a display filter, the glare of the screenwas eliminated, and contrast was improved without darkening the screen.Further, eye fatigue was not noted after looking the display for a longtime.

Similar effects could be obtained when optical apparatus lenses andfilters, and lighting apparatus covers were prepared using the sameprocedure.

(EXAMPLE 17)

100 Parts of polymethylmethacrylate was melted at 200° C., and 10 partsby weight of aquahydroxy(1-thiophenyl-1,3-butanedionato)erbium was addedand uniformly mixed. The mixture was reverted back to room temperatureand then crushed into flakes. The result was molded to a display filterusing an injection molding machine. The molding was transparent andslightly rose-colored, the transmissivity was 20% at 520 nm, blockedultraviolet of less than 400 nm, and transmissivity of other wavelengtharea was about 85%.

When the molding was used as a display filter, glare of the screen waseliminated, and contrast was improved without darkening the screen.Further, eye fatigue was not noted after looking the display for a longtime.

Similar effects could be obtained when optical apparatus lenses andfilters, and lighting apparatus covers were prepared using the sameprocedure.

COMPARATIVE EXAMPLES (Comparative Example 1)

Neodymium oxide, neodymium carbonate, neodymium chloride, neodymiumnitrate, neodymium sulfate, neodymium sulfide, neodymium oxalate,neodymium acetate, and neodymium methacrylate were not soluble inmonomers such as styrene, divinylbenzene, phenylmethacrylate,tetrahydrofurfuryl methacrylate, methylmethacrylate, benzylmethacrylate,diallylphthalate, diethyleneglycolbisallylcarbonate, o-chlorostyrene,and the like.

(Comparative Example 2)

Four grams of trisbenzoylacetonatoneodymium produced by the productionmethod shown below was dissolved in 100 g of toluene and checked forchanges over time under irradiation with a fluorescent lamp. As aresult, the solution, which was initially blue-violet colored, becamegreen with the passage of time, and after 2 weeks, it became yellow andproduced a yellow precipitate.

Production method of trisbenzoylacetonatoneodymium is shown below. 2.43g of benzoylacetone was dissolved in 5% aqueous ammonia solution, andthe benzoylacetone-ammonia water solution was added to an aqueousneodymium acetate solution obtained by dissolving 1.70 g of neodymiumacetate hydrate in 50 ml of water to obtain a crystal of blue-violettrisbenzoylacetonatoneodymium.

(Comparative Example 3)

The photopolymerization composition used in Example 1 was injected intoa cast molding die comprising two glass molds and a plastic gasket, andirradiated continuously for 3 minutes with ultraviolet light of anilluminance of 400 mW/cm² using a 2 KW high-pressure mercury lamp fromboth sides of the molding die to obtain a 2 mm thick highly transparentplate-formed polymer. After the plate-formed polymer was allowed tostand in a high temperature and high humidity environment at 60° C. and90% RH for one week, the water absorption was 1.0%. This was the samevalue as the lens of Example 1 which containedaquahydroxy(1-phenyl-1,3-butanedionato)neodymium. After the plate-formedpolymer was provided on the surface with a reflection-proof film andallowed to stand in the above high temperature and high humidityenvironment for one week, no cracking was noted in the deposited film.

(Comparative Example 4)

Three parts by weight of neodymium acetate was dissolved in 20 parts byweight of methacrylic acid, and mixed with 80 parts by weight of thephotopolymerization composition of Example 1. The mixture was injectedinto a cast molding die comprising two glass molds and a plastic gasket,and irradiated continuously for 3 minutes with ultraviolet light of anilluminance of 400 mW/cm² using a 2 KW high-pressure mercury lamp fromboth sides of the molding die to obtain a 2 mm thick blue-violet coloredhighly transparent plate-formed polymer. The thus obtained plate-formedpolymer had a transmissivity of as low as 30% at 580 nm, and thetransmissivity of other wavelength areas was more than 90%, but did notblock ultraviolet light of less than 400 nm, and after the plate-formedpolymer was allowed to stand in a high temperature and high humidityenvironment at 60° C. and 90% RH for one week, the water absorption wasas high as 5.0%. After the plate-formed polymer was provided on thesurface with an inorganic deposited film as a reflection-proof film andallowed to stand in the above high temperature and high humidityenvironment for one week, cracking was generated in the deposited film.

(Comparative Example 5)

Two parts by weight of neodymium acetate, in place ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium, was dissolved in 15parts by weight of methacrylic acid under heating, mixed with 30.6 partsby weight of styrene, 51 parts by weight of2,2-bis(4-methacroyloxyethoxy-3,5-dibromophenyl)propane, 3.4 parts byweight of diethyleneglycolbisallylcarbonate, and 1 part by weight oft-butylperoxyneodecanoate, and filtered. The filtrate was injected intoa mold comprising two glass molds and a gasket of ethylene-vinyl acetatecopolymer, and polymerized as in Example 2. After polymerization, thelens was released from the molding die. Further, the lens was annealedat 100° C. for 2 hours.

The resulting lens had a transmissivity of as low as 40% at 580 nm, andthe transmissivity of other wavelength areas was more than 85%. However,it did not block ultraviolet light of less than 400 nm. The resultinglens was allowed to stand in a high temperature and high humidityenvironment at 60° C. and 90% RH for one week as in Example 2. As aresult, the water absorption was 3.0% which was 3 times higher thanExample 2, and a negative strength lens generated a curved deflection atthe central portion. After the plate-formed polymer was provided on thesurface with an inorganic deposition film as a reflection-proof film andallowed to stand in the above high temperature and high humidityenvironment for one week, generation of cracking was noted in thedeposition film.

(EXAMPLE 18)

After 36 parts by weight of styrene, 60 parts by weight of2,2-bis(4-methacroyloxyethoxy-3,5-dibromophenyl)propane, 4 parts byweight of diethyleneglycolbisallylcarbonate, and 2 phm ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium of Synthesis Example 2were mixed, 1 phm of t-butylperoxyneodecanoate as an initiator wasadded, further agitated and filtered. The filtrate was injected into amold, comprising two glass flat plates and a gasket of ethylenevinylacetate copolymer,whose clearances are 2 mm, 3 mm, 4 mm, 5 mm, and 10mm.

Then, the filtrate was heated at 30° C. for 4 hours, linearly increasedfrom 30° C. to 50° C. over a period of 10 hours, linearly increased from50° C. to 80° C. in 2 hours, maintained at 80° C. for 1 hour, and cooledto 70° C. in 2 hours.

The gasket was removed, and the resulting molding was separated from theglass flat plates. The resulting molding was annealed at 100° C. for 2hours.

In the same method, flat moldings of 2 mm, 3 mm, 4 mm, and 5 mm inthickness were obtained with a content ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium of 5 phm. Further, flatmolding of 1 mm, 2 mm, and 3 mm in thickness were obtained with acontent of aquahydroxy(1-phenyl-1,3-butanedionato)neodymium of 10 phm.

The thus obtained moldings had high transparency.

Thicknesses of the resulting moldings and the absorbances at 580 nmwhich is the characteristic absorption wavelength of neodymium atom areshown in FIG. 7.

The results show that when the thickness of the molding is to bereduced, sufficient objective effects (glare-proof effect, eye fatigueprevention effect) can be obtained by increasing the content of thetwo-coordination complex.

(EXAMPLE 19)

To a mixture comprising 45 parts by weight of a mixture of2,2'-(p-xylene-a,a'-dithio)diethyldimethacrylate of the followingFormula (a) and 2-4-(2-hydroxyethylthiomethylene)benzylthio!ethylmethacrylate of thefollowing Formula (b), 10 parts by weight of benzylmethacrylate, 10parts by weight of methylmethacrylate, 10 parts by weight ofisobornylmethacrylate, and 25 parts by weight oftetraethyleneglycoldimethacrylate, 20000 ppm of2,4-diphenyl-4-methyl-1-petene (Nippon Yushi: NOFMER MSD) as a radicalpolymerization controller, 2000 ppm of hindered amine typephotostabilizer LA63P (Asahi Denka) as a photostabilizer, and 2000 ppmof trisisodecylphosphite (Asahi Denka: MARK 3010) as an antioxidant wereadded and mixed.

To the mixture, 5 phm ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium of the SynthesisExample and 5 phm of aquahydroxy(1-phenyl-1,3-butanedionato)erbium wereadded, and 0.2 phm of t-butylperoxyneodecanoate and 0.6 phm oft-butylperoxyisobutyrate as radical polymerization initiators werefurther added and mixed. The resulting mixture was filtered, and thefiltrate was injected into a cast molding die comprising two glass moldsand a gasket of ethylene-vinyl acetate copolymer to obtain of 2 mm ofcenter thickness.

Then, the molding die was heated at 30° C. for 10 hours, linearlyincreased from 30° C. to 40° C. in 3 hours, linearly increased from 40°C. to 45° C. in 2 hours, from 45° C. to 55° C. in 1 hour, from 55° C. to70° C. in 1 hour, from 70° C. to 100° C. in 2 hours, maintained at 100°C. for 2 hours, and cooled from 100° C. to 70° C. in 2 hours.

The gasket was removed from the cast molding die comprising the gasketand the glass molds, and the resin molding was separated from the glassmolds. The resulting resin molding was annealed at 100° C. for 2 hours.

The resulting lens had a refractive index of 1.55, the lighttransmissivity was as low as 18% at 520 nm and 580 nm, blockedultraviolet light of less than 400 nm in wavelength, and transmissivityof other wavelength area was more than 85%. Therefore, the lens was onewhich had a superior glare-proof function to selectively block or reduceonly light of a specific wavelength but did not reduce other visiblelight both in light adaptation sight and in dark adaptation sight, andblocked ultraviolet light. The lens showed an achromatic gray undersunlight, pale green under a fluorescent lamp, and pale rose under anincandescent lamp.

Further, after the lens was allowed to stand in a high temperature andhigh humidity environment at 60° C. and 90% RH for one week, the waterabsorption was 1.0%, which was fairly good. After the lens was providedon the surface with an inorganic deposition film as a reflection-prooffilm and allowed to stand in the above high temperature and highhumidity environment for one week, no cracking was noted in thedeposition film. The transmissivity in the area other than 520 nm and580 nm was 99%.

When letters, a still picture, and an animation on a CRT display screenwere viewed through the lens, glare on the screen was eliminated, andthe contrast was improved without darkening the screen. ##STR17##

(EXAMPLE 20)

To a mixture comprising 45 parts by weight of a mixture of2,2'-(p-xylene-a,a'-dithio)diethyldimethacrylate of the followingFormula (a) and 2-4-(2-hydroxyethylthiomethylene)benzylthio!ethylmethacrylate of thefollowing Formula (b), 10 parts by weight of benzylmethacrylate, 20parts by weight of isobornylmethacrylate, and 25 parts by weight oftetraethyleneglycoldimethacrylate, 20000 ppm of4-diphenyl-4-methyl-1-pentene (Nippon Yushi: NOFMER MSD) as a radicalpolymerization controller, 2000 ppm of hindered amine typephotostabilizer LA63P (Asahi Denka) as a photostabilizer, and 2000 ppmof trisisodecylphosphite (Asahi Denka: MARK 3010) as an antioxidant wereadded and mixed.

To the mixture, 3 phm ofaquahydroxy(1-phenyl-1,3-butanedionato)neodymium of Synthesis Example 1and 3 phm of aquahydroxy(1-phenyl-1,3-butanedionato)erbium were added,and 0.2 phm of t-butylperoxyneodecanoate and 0.6 phm oft-butylperoxyisobutyrate as radical polymerization initiators werefurther added and mixed. The resulting mixture was filtered, and thefiltrate was injected into a cast molding die comprising two glass moldsand a gasket of ethylene-vinyl acetate copolymer to obtain lenses of 2mmof center thickness. Then, the molding die was heated at 30° C. for 10hours, linearly increased from 30° C. to 40° C. in 3 hours, linearlyincreased from 40° C. to 45° C. in 2 hours, from 45° C. to 55° C. in 1hour, from 55° C. to 70° C. in 1 hour, from 70° C. to 100° C. in 2hours, maintained at 100° C. for 2 hours, and cooled from 100° C. to 70°C. in 2 hours.

The gasket was removed from the cast molding die comprising the gasketand the glass molds, and the resin molding was separated from the glassmolds. The resulting resin molding was annealed at 100° C. for 2 hours.

The resulting lens had a refractive index of 1.55, the lighttransmissivity was as low as 36% at 520 nm and 580 nm, blockedultraviolet light of less than 400 nm in wavelength, and thetransmissivity of other wavelength areas was more than 85%. Therefore,the lens was one which had a superior glare-proof function toselectively block or reduce only light of a specific wavelength but didnot reduce other visible light both in light adaptation sight and indark adaptation sight, and blocked ultraviolet light. The lens showed anachromatic gray color under sunlight, pale green under a fluorescentlamp, and pale rose tinder an incandescent lamp.

Further, after the lens was allowed to stand in a high temperature andhigh humidity environment at 60° C. and 90% RH for one week, the waterabsorption was 1.0%, which was fairly good. After the lens was providedon the surface with an inorganic deposited film as a reflection-prooffilm and allowed to stand in the above high temperature and highhumidity environment for one week, no cracking was noted in thedeposited film. The transmissivity in the area other than 520 nm and 580nm was 99%.

When letters, a still picture, and an animation on a CRT display screenwere viewed through the lens, glare on the screen was eliminated, andthe contrast was improved without darkening the screen.

(EXAMPLE 21)

The mixture prepared in Example 20 was injected into a cast molding diecomprising a glass mold for progressive multiple focus lens (SEIKOPLACKS II GXP-1S) as a farsighted eyeglass lens and a gasket ofethylene-vinyl acetate copolymer. The molding die was treated using thesame procedure as in Example 20 to obtain a resin-based progressivemultiple focus lens. The resulting lens was annealed for 2 hours, andprovided on the surface with an inorganic deposition film as areflection-proof film.

The lens of the present example was attached to an eyeglass frame andsubjected to a wearing test. The test was conducted by the same methodas in Example 5. As a comparison, a lens of the same composition asExample 20 except that aquahydroxy(1-phenyl-1,3-butanedionato)neodymiumand aquahydroxy(1-phenyl-1,3-butanedionato)erbium were removed, dyed tothe same color (gray) as the lens of the present example, and providedwith a reflection-proof film, was used. The results are shown in Table10.

                  TABLE 10                                                        ______________________________________                                                   Example 21      Comparative                                        Item         Average Variance  Average                                                                             Variance                                 ______________________________________                                        Glare reduction                                                                            4.80    0.2       2.90  0.2                                      Eye fatigue prevention                                                                     4.90    0.1       2.88  0.1                                      Lightness of sight                                                                         4.40    0.3       4.33  0.3                                      Contrast     4.80    0.2       2.80  0.2                                      ______________________________________                                    

(EXAMPLE 22)

To a composition comprising:

    ______________________________________                                        Isocyanurate derivative having a triazine                                                               70 parts                                            skeleton and metharylic group in the molecule                                                           by weight                                           of the following Formula (a)                                                  Benzyl methacrylate       30 parts                                                                      by weight                                           t-Butylperoxyneodecanoate 0.5 phm                                             ______________________________________                                    

butanedionato)neodymium was added, mixed and dissolved, and filtered.The filtrate was injected into a molding die comprising two glass moldsand a gasket of ethylene-vinyl acetate copolymer to obtain lenses of 2mm of center thickness.

Then, the molding die was heated at 30° C. for 5 hours, increased from30° C. to 80° C. over a period of 10 hours, maintained at 80° C. for 2hours, cooled from 80° C. to 70° C. in 2 hours, and the molding wasreleased from the molding die. The resulting molding was annealed at100° C. for 2 hours.

The light transmissivity of the resulting molding was as low as 20% at580 nm, blocked ultraviolet light of less than 400 nm in wavelength, andtransmissivity of other wavelength area was more than 85%. ##STR18##

(EXAMPLE 23)

To a composition comprising:

    ______________________________________                                        Polyester methacrylate of the following                                                                 60 parts                                            Formula (b)               by weight                                           Ethyleneglycol dimethacrylate of Formula (c)                                                            20 parts                                                                      by weight                                           Benzyl methacrylate       10 parts                                                                      by weight                                           t-Butylperoxyneodecanoate 0.5 phm                                             ______________________________________                                    

5 parts by weight of aquahydroxy(1-phenyl-1,3-butanedionato)neodymiumwas added, mixed and dissolved, and filtered.

The filtrate was injected into a molding die comprising two glass moldsand a gasket of ethylene-vinyl acetate copolymer to obtain lenses of 2mm of center thickness.

Then, the molding die was heated at 30° C. for 5 hours, increased from30° C. to 80° C. over a period of 10 hours, maintained at 80° C. for 2hours, cooled from 80° C. to 70° C. in 2 hours, and the molding wasreleased from the molding die. The resulting molding was annealed at100° C. for 2 hours.

The light transmissivity of the resulting molding was as low as 20% at580 nm, blocked ultraviolet light of less than 400 nm in wavelength, andtransmissivity of other wavelength area was more than 85%. ##STR19##

(EXAMPLE 24)

The flat-formed molding obtained in Example 18 was attached to aneyeglass frame, used by randomly extracted 50 men and 50 women engagedin VDT work, and eye fatigue when conducted a wordprocessor input work(VDT work) of 5000 characters was evaluated in a 5-grade method.

The test results are shown in FIG. 8 and FIG. 9.

Questions for evaluation were set as follows.

5 points: feel considerable eye fatigue (e.g. eye pain, dim sight,etc.).

4 points: between 3 and 5.

3 points: feel an eye fatigue.

2 points: between 1 and 3.

1 point: feel almost no eye fatigue.

0 point: feel no eye fatigue at all.

UTILIZABILITY IN INDUSTRY

The transparent plastic material of the present invention is useful foreyeglass lenses, contact lenses, intraocular lenses, sunglasses, displayfilter covers, lighting apparatus covers, automotive mirrors, andoptical apparatus lenses and filters for cameras. Further, the materialis also used as a hard copy for eyeglass lenses and optical apparatuslenses.

We claim:
 1. A transparent plastic material comprising a polymerobtained by polymerizing one or more polymerizable monomers in thepresence of a polymerization initiator or polymerization catalyst,wherein said polymer contains a complex compound of Formula (I),

    A.sub.2 M(OH)(H.sub.2 O)                                   (I)

wherein M denotes Sc, Y, La, Pt, Nd, Pm, Sm, Gd, Dy, Ho, Er, Tm, or Lu;A is a ligand for forming a chelate complex having a basic structureshown below, ##STR20## and containing at least one of an aryl group anda heterocyclic group.
 2. The transparent plastic material of claim 1,wherein said polymerizable monomer contains a radical polymerizablegroup.
 3. The transparent plastic material of claim 1, wherein saidpolymerizable monomer contains a polyaddition polymerizable group. 4.The transparent plastic material of claim 1, wherein said polymerizablemonomer contains a polycondensation polymerizable group.
 5. An opticalarticle comprising the transparent plastic material of claim
 1. 6. Theoptical article of claim 5, wherein said optical article is an eyeglasslens.
 7. The optical article of claim 5, wherein said optical article isa farsighted eyeglass lens.
 8. The optical article of claim 5, whereinsaid optical article is a contact lens.
 9. The optical article of claim5, wherein said optical article is a display filter.
 10. The opticalarticle of claim 5, wherein said optical article is an optical apparatuslens or filter.
 11. The optical article of claim 5, wherein a thin filmlayer of said polymer of claim 1 is formed on a substrate comprising atransparent plastic material.
 12. The optical article of claim 11,wherein said substrate comprising a transparent plastic material is anoptical apparatus lens or a filter including an eyeglass lens,sunglasses, display filter cover, a lighting apparatus cover, anautomotive mirror, and a camera.
 13. The transparent plastic material ofclaim 1, wherein said polymer comprises a styrene transparent plasticmaterial comprising styrene and/or a styrene derivative.
 14. Thetransparent plastic material of claim 1, wherein said polymer comprisesan isocyanurate transparent plastic material comprising an isocyanuratederivative having a triazine skeleton and a radical polymerizable groupin the molecule.
 15. The transparent plastic material of claim 1,wherein said polymer comprises a urethane(meth)acrylate transparentplastic material comprising an urethane(meth)acrylate obtained byreacting an isocyanate group containing compound with a hydroxy groupcontaining compound.
 16. The transparent plastic material of claim 1,wherein said polymer comprises a polyester(meth)acrylate transparentplastic material comprising a polyester(meth)acrylate having a polyesterstructure in the molecule.
 17. The transparent plastic material of claim2, wherein said polymer is obtained by polymerizing a compositioncomprising a (meth)acrylic monomer containing sulfur in the molecule.18. An optical article comprising a polymer obtained by polymerizing aradical polymerizable monomer comprising 40 to 60 parts by weight of a(meth)acrylate containing a sulfur atom in the molecule of Formula (II),##STR21## wherein R is a hydrogen atom or a methyl group, X is a sulfuratom or an oxygen atom, and n is an integer from 0 to 3, 10 to 30 partsby weight of an aliphatic (meth)acrylate, and 10 to 30 parts by weightof polyethyleneglycoldimethacrylate in the presence of a radicalpolymerization initiator, wherein said polymer comprises a transparentplastic material containing a complex compound of Formula (I) andwherein said optical article is an eyeglass lens

    A.sub.2 M(OH)(H.sub.2 O)                                   (I)

wherein M denotes Sc, Y, La, Pt, Nd, Pm, Sm, Gd, Dy, Ho, Er, Tm, or Lu;A is a ligand for forming a chelate complex having a basic structureshown below, ##STR22## and containing at least one of an aryl group anda heterocyclic group.
 19. The optical article of claim 18, wherein M ofsaid complex compound of Formula (I) is one of Nd, Er, and Ho, and acontent thereof is 2 to 15 phm based on the polymerizable monomer. 20.The optical article of claim 19, wherein M of said complex compound ofFormula (I) is Nd and Er, and a content thereof is 2 to 15 phm eachbased on the polymerizable monomer.
 21. The optical article of claim 19,wherein M of said complex compound of Formula (I) is Nd, Er, and Ho, anda content thereof is 2 to 15 phm each based on the polymerizablemonomer.
 22. The transparent material of claim 1 produced bypolymerizing (1) one or more polymerizable monomers in the presence of(2) a polymerization initiator or a polymerization catalyst.
 23. Thetransparent material of claim 22 produced, by changing a compositioncontaining (1) one or more polymerizable monomers, (2) a polymerizationinitiator or a polymerization catalyst and (3) said complex compound ofFormula (I) is into a mold, and polymerizing said composition in themold.
 24. The transparent material of claim 22, produced by polymerizinga composition containing (1) one or more polymerizable monomers, (2) apolymerization initiator or a polymerization catalyst thereafter meltingthe product, the molten product is mixed with (3) a complex compound ofFormula (I) for uniform dissolution and is solidified, and thesolidified product is remelted and resolidified in a mold of a moldingmachine to obtain the polymer.
 25. The transparent material of claim 22,produced by polymerizing a composition containing (1) one or morepolymerizable monomers and (2) a polymerization initiator or apolymerization catalyst mixed with (3) said complex compound of Formula(I) and resolidifying of such.
 26. The transparent material of claim 22,produced by polymerizing a composition containing (1) one or morepolymerizable monomers, (2) a polymerization initiator or apolymerization catalyst, and (3) said complex compound of Formula (I),andthereafter, melting the polymerization product and then solidifiedsuch in a mold of a molding machine.
 27. The transparent plasticmaterial of claim 1, wherein said polymer is obtained by polymerizing acomposition comprising a multifunctional (meth)acrylic monomer.
 28. Thetransparent plastic material of claim 27, wherein said multifunctional(meth)acrylic monomer contains sulfur in the molecule.
 29. Thetransparent plastic material of claim 28, wherein said multifunctional(meth)acrylic monomer containing sulfur in the molecule is a monomer ofFormula (a): ##STR23##
 30. The transparent plastic material of claim 29,wherein said composition further comprises an aromatic (meth)acrylateand tetraethyleneglycol di(meth)acrylate.
 31. The transparent plasticmaterial of claim 30, wherein said aromatic (meth)acrylate is selectedfrom the group consisting of benzyl(meth)acrylate andisobornyl(meth)acrylate.